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WO2000025736A1 - Aerosol device containing a condensation polymer comprising at least a polyurethane and/or polyurea unit - Google Patents

Aerosol device containing a condensation polymer comprising at least a polyurethane and/or polyurea unit Download PDF

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Publication number
WO2000025736A1
WO2000025736A1 PCT/FR1999/002585 FR9902585W WO0025736A1 WO 2000025736 A1 WO2000025736 A1 WO 2000025736A1 FR 9902585 W FR9902585 W FR 9902585W WO 0025736 A1 WO0025736 A1 WO 0025736A1
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WO
WIPO (PCT)
Prior art keywords
chosen
copolymers
diisocyanate
acid
group
Prior art date
Application number
PCT/FR1999/002585
Other languages
French (fr)
Inventor
Arnaud Vilbert
Original Assignee
L'oreal
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=9532304&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2000025736(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by L'oreal filed Critical L'oreal
Priority to DK99950819T priority Critical patent/DK1043969T3/en
Priority to PL341481A priority patent/PL198093B1/en
Priority to DE69936253T priority patent/DE69936253T3/en
Priority to CA002316398A priority patent/CA2316398C/en
Priority to AU63455/99A priority patent/AU746529B2/en
Priority to EP99950819A priority patent/EP1043969B2/en
Priority to JP2000579180A priority patent/JP3646149B2/en
Publication of WO2000025736A1 publication Critical patent/WO2000025736A1/en
Priority to US12/633,236 priority patent/US8691200B2/en
Priority to US12/722,656 priority patent/US20100172857A1/en

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Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/06Preparations for styling the hair, e.g. by temporary shaping or colouring
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/046Aerosols; Foams
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/87Polyurethanes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/90Block copolymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/0804Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633Compounds of group C08G18/42
    • C08G18/6659Compounds of group C08G18/42 with compounds of group C08G18/34
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/59Mixtures
    • A61K2800/594Mixtures of polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/87Application Devices; Containers; Packaging

Definitions

  • the subject of the invention is pump bottle devices comprising a reservoir which contains, in a cosmetically acceptable medium, a multiblock polymer (A) comprising at least one polyurethane and / or polyurea unit and a film-forming polymer (B), the polymers (A) and (B) and the device being chosen so as to obtain, at the outlet of the device, droplets of composition with an average diameter of less than 80 ⁇ m. It also relates to a method for shaping or maintaining the hairstyle comprising the implementation of these devices as well as their use for the manufacture of a styling product.
  • the fixing of the hairstyle is an important element of the styling which consists in maintaining the shaping already carried out or in shaping the hair and in fixing them simultaneously.
  • the most widespread haircare products for shaping and / or maintaining the hairstyle on the cosmetics market are spray compositions essentially consisting of a solution, most often alcoholic and / or aqueous and of a or several materials, generally polymer resins, the function of which is to form welds between the hair / also called fixing materials, in admixture with various cosmetic adjuvants.
  • This solution can be packaged for example in a pump bottle.
  • the compositions for fixing the hairstyle must release less and less volatile organic compounds (VOC).
  • VOC volatile organic compounds
  • this modification of the formulation of the hair compositions has the harmful effect of greatly increasing their viscosity.
  • Packaging in the form of a pump bottle is especially practical for the user, who can easily dose the quantity of product he wishes to apply.
  • this type of packaging sometimes makes it difficult to apply the product evenly to the hair, since the droplets of product leaving the pump bottle are often too large. This drawback is particularly marked for viscous compositions for which fine droplets are difficult to obtain.
  • the quality of the spraying obtained by means of a pump-bottle device that is to say essentially the distribution of the droplets in the space at the outlet of the nozzle, strongly depends on the chemical constitution of the composition used. . There is therefore a very particular interest in the production of pump bottle devices which give rise to fine droplets, despite the high viscosity of the compositions.
  • the subject of the invention is a pump bottle device comprising a reservoir containing a hair composition as well as means for dispensing the composition, characterized in that: (1) the composition comprises, in a cosmetically acceptable medium, at least one polycondensate (A) comprising at least one polyurethane and / or polyurea block and at least one film-forming polymer (B) different from (A);
  • the polymers (A) and (B) and the device being chosen so as to obtain, at the outlet of the device, droplets of composition with an average diameter less than or equal to 80 ⁇ m.
  • Another object of the invention relates to a method for shaping or maintaining the hairstyle comprising the use of this pump-flask device.
  • Yet another object of the invention relates to the use of this device for the manufacture of a styling product.
  • polycondensates comprising at least one polyurethane and / or polyurea block which are particularly targeted by the present invention are those described in patents EP 0 751 162, EP 0 637 600, FR 2 743 297 and EP 0 648 485 of which the Applicant is the Holder, as well that EP 0 656 021 or WO 94/03510 from BASF and EP 0 619 111 from National Starch.
  • the polycondensates used in accordance with the invention may be soluble in the cosmetically acceptable medium, in particular after neutralization with an organic or inorganic base, or else form a dispersion in this medium.
  • the dispersion can then comprise at least 0.05% of surfactant enabling the polycondensate to be dispersed and maintained in dispersion.
  • any type of surfactant can be used in said dispersion, but preferably a nonionic surfactant.
  • the average particle size of the polycondensate in the dispersion is preferably between 0.1 and 1 micron.
  • the polycondensate can be formed by an arrangement of blocks, this arrangement being obtained in particular from:
  • the compounds (1) are chosen from the group comprising diols, diami ⁇ es, polyesterols, polyetherols or their mixture.
  • the compounds (1) which are preferred are linear polyethylene and polypropylene glycols, in particular those obtained by reaction of ethylene or propylene oxide with water or of diethylene or dipropylene glycol in the presence of sodium hydroxide as a catalyst.
  • These polyglycols generally have a molecular weight of between about 600 and 20,000.
  • polyhydroxy compounds such as polyether diols, polyester diols, - polyacetal diols, polyamide diols, polyester polyamide diols, poly (alkylene ether) diols, polythioether diols and polycarbonate diols.
  • the preferred polyether diols are, for example, the condensation products of ethylene oxide, propylene oxide or tetrahydrofuran, their copolymerization or condensation products, grafted or block, such as mixtures of oxide condensates ethylene and propylene, and the polymerization of olefins, under high pressure, with alkylene oxide condensates.
  • Suitable polyethers are for example prepared by conden- sation of alkylene oxides and polyhydric alcohols, such as ethylene glycol, 1,2-propylene glycol and 1,4-butanediol.
  • polyester diols, polyester amides and polyamide diols are preferably saturated and are obtained, for example, from the reaction of saturated or unsaturated pofycarboxylic acids with polyhydric alcohols, diamines or polyamines.
  • polyhydric alcohols suitable for preparing polyesters include, for example, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, neopentyl glycol and hexane diol.
  • amino alcohols for example ethanolami ⁇ e.
  • Diamines suitable for preparing polyester amides are ethylene diamine and hexamethylene diamine.
  • Suitable polyacetals can be prepared, for example, from 1,4-butanediol or hexanediol and formaldehyde.
  • Suitable polythioethers can be prepared, for example, by condensation reaction between thioglycols either alone or in combination with other glycols such as ethylene glycol, 1,2-propylene glycol or with other polyhydroxy compounds.
  • Polyhydroxy compounds already containing urea or urethane groups, natural polyols, which can be further modified, for example, beaver oil and carbohydrates can also be used.
  • the compound of group (1) is a polyesterol, in particular a polyester diol formed by the reaction of at least one (di) -polyol (1 a ) and at least one acid (1 b ).
  • the (di) - polyol (1 a ) is in particular chosen from the group comprising ⁇ éopentylglycol, 1,4-butanediol, hexanediol, ethylene-glycol, diethylene glycol, propylene glycol, butylene glycol, neopen - tyiglycol and (di) -polyethylene glycol.
  • the acid ( 1b ) is in particular chosen from the group comprising phthalic acid, isophthalic acid, adipic acid and (poly) -lactic acid.
  • compound (2) it is possible in particular to use a hydroxycarboxylic acid such as dimethylol propanoic acid (DMPA) or a carboxylic acid 2,2-hydroxymethyl.
  • DMPA dimethylol propanoic acid
  • compound (2) is useful as a coupling block.
  • compounds (2) preferred are those comprising at least one poly (acid- (alpha-hydroxycarboxyliquediol)).
  • the compounds (2) which are particularly preferred in accordance with the invention are those chosen from the group comprising 2,2-di- (hydroxymethyl) acetic acid, 2,2-dihydroxymethyl propionic acid, 2,2-dihydroxymethyl butyric acid, 2,2-dihydroxymethyl pentanoic acid.
  • the di- or polyisocyanate (3) can be chosen in particular from the group comprising hexamethylene diisocyanate, isophorondiisocyanate (IDPI), toluylendiisocyanate, diphenylmethane 4,4'-diisocyanate (DPMD) and dicy-clohexylmethane 4, 4'-diisocyanate (DCMD), methylene-di-p-phenyl diisocyanate, methylene-bis (4-cyclohexylisocyanate), isophorone diisocyanate, toluene diisocyanate, 1,5-naphthalene diisocyanate, 4,4 ' -diphenylmethane diisocyanate, 2,2'-dimethyl-4,4'-diphenylmethane diisocyanate, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, mixtures of 2,4- and 2,6-tolu
  • the polycondensate can be formed using an additional compound
  • These compounds (4) can be chosen from the group comprising in particular saturated or unsaturated glycols such as ethylene glycol, diethylene glycol, neopentyl glycol, triethylene glycol, amino alcohols such as ethanolamine, propanoinamine , butanolamine, primary heterocyclic, aromatic, cycloaliphatic, and aliphatic amines, diamines, carboxyic acids such as aliphatic, aromatic, heterocyclic carboxylic acids such as acid oxalic, succinic, glutaric, adipic, sebacic, terephthalic, aminocarboxylic acids.
  • the preferred compounds (4) are the aliphatic diols.
  • the polycondensates in accordance with the invention can also be formed from additional compounds (5) having a silicone skeleton such as polysiloxanes, polyalkylsiloxanes or polyarylsiloxanes, in particular polyethylsiloxanes, polymethylsiloxanes and polyphenylsiloxanes, optionally comprising hydrocarbon chains grafted onto silicon atoms.
  • additional compounds (5) having a silicone skeleton such as polysiloxanes, polyalkylsiloxanes or polyarylsiloxanes, in particular polyethylsiloxanes, polymethylsiloxanes and polyphenylsiloxanes, optionally comprising hydrocarbon chains grafted onto silicon atoms.
  • polyurethane and / or polyurea blocks of the polymer advantageously used have a basic repeating unit corresponding to the general formula below:
  • - X ' represents 0 and / or NH
  • - B is a bivalent hydrocarbon radical, this radical being substituted or not
  • R is a divalent radical chosen from alkylene radicals of aromatic type, aliphatic C l -C 2 o cycloaliphatic Ci -C 20, these radicals being substituted or unsubstituted.
  • the radical B is a C 1 to C 30 radical and carries a group having one or more carboxylic function (s) and / or one or more sulfonic functions, said carboxylic and / or sulfonic functions being in free form or partially or totally neutralized with a mineral or organic base.
  • the radical R is advantageously chosen from the radicals corresponding to the following formulas:
  • b is an integer between 0 and 3
  • c is an integer between 1 and 20, preferably between 2 and 12.
  • radical R is chosen from hexamethylene radicals
  • polycondensate used according to the invention comprising at least one polyurethane and / or polyurea block can advantageously further comprise at least one polysiloxane block whose basic repeating unit corresponds for example to the general formula (II ′) below :
  • - P is a polysiloxane segment
  • - X ' represents O and / or NH
  • - R is a divalent radical chosen from alkylene radicals of aromatic, aliphatic C 1 -C 20 , cycloaliphatic C 1 to C 20 type , these radicals being substituted or unsubstituted.
  • polysiloxane segment P corresponds to the general formula below:
  • the radicals A which may be identical or different, are chosen from on the one hand the monovalent hydrocarbon radicals in d to C 20 free or substantially free of ethylenic unsaturation and, on the other hand, the aromatic radicals, - Y represents a bivalent hydrocarbon radical, and - z represents an integer, chosen such that the average molecular weight of the polysiloxane segment is between 300 and 10,000.
  • the bivalent radical Y is chosen from alkylene radicals of formula - (CH 2 ) a -, in which a represents an integer which can be between 1 and 10.
  • the radicals A can be chosen from alkyl radicals, in particular methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl and octadecyl radicals, cycloalkyl radicals, in particular cyclohexyl radical, aryl radicals , in particular phenyl and naphthyl, the arylalkyl radicals, in particular benzyl and phenylethyl, as well as the tolyl and xylyl radicals.
  • the cationic, anionic, amphoteric and nonionic film-forming polymers (B) which can be used in accordance with the invention are described below.
  • the cationic film-forming polymers which can be used according to the present invention are preferably chosen from polymers comprising primary, secondary, tertiary and / or quaternary amine groups forming part of the polymer chain or directly linked to it, and having a molecular weight of between 500 and around 5,000,000 and preferably between 1,000 and 3,000,000.
  • R3 denotes a hydrogen atom or a CH3 radical
  • A is a linear or branched alkyl group of 1 to 6 carbon atoms or a hydroxyalkyl group of 1 to 4 carbon atoms;
  • R5. R ⁇ i identical or different, represent an alkyl group having from 1 to 18 carbon atoms or a benzyl radical; Rl and R2 represent hydrogen or an alkyl group having from 1 to 6 carbon atoms;
  • X denotes a methosulfate anion or a halide such as chloride or bromide.
  • the copolymers of family (1) also contain one or more units deriving from comonomers which can be chosen from the family of acrylamides, methacrylamides, diacetones, acrylamides, acrylamides and methacrylamides substituted on nitrogen by lower alkyls, acrylic acids or mixed - thacryic or their esters, vinyllactams such as vinyipyrroiidone or vinylcaprolactam, vinyl esters.
  • chitosans or their salts are in particular the acetate, lactate, glutamate, gluconate or the pyrrolidone carboxylate of chitosan.
  • chitosan having a deacetylation rate of 90.5% by weight sold under the name KYTAN BRUT STANDARD by the company ABER TECHNOLOGIES
  • the chitosan pyrrolidone carboxylate sold under the name KYTAMER PC by the company AMERCHOL.
  • cationic cellulose derivatives such as copolymers of cellulose or of cellulose derivatives grafted with a water-soluble monomer comprising a quaternary ammonium, and described in particular in US Pat. No. 4,131,576, such as hydroxyalkyl celluloses, such as hydroxymethyl- , hydroxyethyl- or hydroxypropyl celluloses grafted in particular with a salt of methacryloyloxyethyl trimethylammonium, methacryiamidopropyl trimethylammonium, dimethyl-diallylammonium.
  • the marketed products meeting this definition are more particularly the products sold under the name "CELQUAT L 200" and "CELQUAT H 100" by the National Starch Company.
  • Anionic film-forming polymers generally used are polymers containing groups derived • carboxylic acid, sulforiique or phosphoric acid and have a molecular weight between about 500 and 5,000,000.
  • the carboxylic groups are provided by mono or unsaturated dicarboxylic acid monomers such as those corresponding to the formula:
  • n is an integer from 0 to 10
  • Ai denotes a methylene group, optionally linked to the carbon atom of the unsaturated group or to the neighboring methylene group when n is greater than 1 via a heteroatom such as oxygen or sulfur
  • R7 denotes a hydrogen atom, a phenyl or benzyl group
  • R ⁇ denotes a hydrogen atom, a lower alkyl or carboxyl group
  • Rg denotes a hydrogen atom, a lower alkyl group, a -CH2-COOH group, phenyl or benzyl;
  • a lower alkyl radical preferably denotes a group having 1 to 4 carbon atoms and in particular, methyl and ethyl.
  • anionic film-forming polymers with carboxylic groups preferred according to the invention are:
  • C) copolymers derived from crotonic acid such as those comprising in their chain vinyl acetate or propionate units and optionally other monomers such as allyl or methallyl esters, vinyl ether or vinyl ester of a linear or branched saturated carboxylic acid with a long hydrocarbon chain such as those containing at least 5 carbon atoms, these polymers possibly being grafted and crosslinked or else a vinyl, allyl or methallyl ester of a carboxylic - or ⁇ -cyclic acid.
  • Such polymers are described inter alia in French patents 1,222,944, 1,580,545, 2,265,782, 2,265,781, 1,564,110 and 2,439,798. Commercial products falling into this class are resins 28-29-30, 26-13-14 and 28-13-10 sold by the company NATIONAL STARCH.
  • copolymers comprising (i) one or more maleic, fumaric, itaconic acids or anhydrides and (ii) at least one monomer chosen from vinyl esters, vinyl ethers, vinyl halides, phenyivinyl derivatives, acrylic acid and its esters, the anhydride functions of these copolymers being optionally monoesterified or monoamidified.
  • Such polymers are described in particular in US patents 2,047,398, 2,723,248, 2,102,113, GB patent 839,805 and in particular those sold under the names GANTREZ AN or ES by the company ISP.
  • copolymers comprising (i) one or more maleic, citric, itaconic anhydrides and (ii) one or more monomers chosen from allyl or methallyl esters optionally comprising one or more acrylamide, methacrylamide, ⁇ -olefin groups, esters acrylic or methacrylic, acrylic or methacrylic or vinyipyrroiidone acids in their chain, the anhydride functions of these copolymers being optionally monoesterified or monoamidified.
  • these polymers are for example described in French patents 2,350,384 and 2,357,241 of the applicant.
  • the polymers comprising the sulphonic groups are polymers comprising vinyl sulphonic, sulphonic styrene, sulphonic naphthalene or alkyl sulphonic acrylamido units.
  • These polymers can in particular be chosen from:
  • the anionic film-forming polymers are preferably chosen from acrylic acid copolymers such as the acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymer sold under the name ULTRAHOLD STRONG by the company BASF, the copolymers derived from crotonic acid such as the vinyl acetate / vinyl tert-butyl benzoate / crotonic acid terpolymers and the crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers sold under the name Resin 28-29-30 by the company NATIONAL STARCH, polymers derived from maleic, fumaric or itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters such as the methylvinylether / maleic anhydride copolymer mono esterified sold under the name GANTREZ
  • the most particularly preferred anionic film-forming polymers are chosen from the methyl ester / mono esterified maleic anhydride copolymer sold under the name GANTREZ ES 425 by the company ISP, the acrylic acid / ethyl acrylate / N-tertiobutylacrylamide terpolymer sold under the name ULTRAHOLD STRONG by the company BASF, the copolymers of methacrylic acid and methyl methacrylate sold under the name EUDRAGIT L by the company ROHM PHARMA, the vinyl acetate / tert-butyl vinyl benzoate / crotonic acid terpolymers and the crotonic acid / acetate terpolymers of vinyl / vinyl neododeca ⁇ oate sold under the name Resin 28-29-30 by the company NATIONAL STARCH, the copolymer of methacrylic acid and ethyl acrylate sold under the name LUVIMER MAEX OR MAE
  • amphoteric film-forming polymers which can be used in accordance with the invention can be chosen from polymers comprising units B and C distributed statistically in the polymer chain where B denotes a unit derived from a monomer comprising at least one basic nitrogen atom and C denotes a unit deriving from an acidic monomer comprising one or more carboxylic or sulphonic groups or else B and C may denote groups deriving from zwitterionic monomers of carboxybetaines or of sulfobetaines;
  • B and C can also denote a catalytic polymer chain comprising primary, secondary, tertiary or quaternary amine groups, in which at least one of the amine groups carries a carboxylic or sulphonic group linked via a hydrocarbon radical or else B and C are part of a chain of a polymer with an ethylene unit ⁇ , ⁇ - dicarboxylic acid, one of the carboxyl groups of which has been reacted with a polyamine comprising one or more primary or secondary amine groups.
  • amphoteric film-forming polymers corresponding to the definition given above which are more particularly preferred are chosen from the following polymers:
  • a monomer derived from a vinyl compound carrying a carboxylic group such as more particularly acrylic acid, methacrylic acid, maleic acid, alpha-chloroacrylic acid, and d 'a basic monomer derived from a substituted vinyl compound containing at least one basic atom
  • dialkylaminoalkylmethacrylate and acrylate the dialkylaminoalkylmethacrylamide and acrylamide.
  • polymers comprising units derived from: a) at least one monomer chosen from acrylamides or methacrylamides substituted on nitrogen by an alkyl radical, b) from at least one acidic comonomer containing one or more carboxylic groups reagents, and c) at least one basic comonomer such as esters with primary, secondary, tertiary and quaternary amine substituents of acrylic and methacrylic acids and the product of quaternization of dimethylaminoethyl methacrylate with dimethyl sulfate or diethyl.
  • the N-substituted acrylamides or methacrylamides which are more particularly preferred according to the invention are groups whose alkyl radicals contain from 2 to 12 carbon atoms and more particularly N-ethylacrylamide, N-tertiobutyl acrylamide, N-tertiooctyl acrylamide, N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide as well as the corresponding methacrylamides.
  • the acid comonomers are chosen more particularly from acrylic, methacrylic, crotonic, itaconic, maleic, fumaric acids as well as alkyl monoesters having 1 to 4 carbon atoms of maleic or fumaric acids or anhydrides.
  • the preferred basic comonomers are aminoethyl, butyl aminoethyl, N, N'-dimethylaminoethyl, N-tert-butylaminoethyl methacrylates.
  • Copolymers are particularly used whose name CTFA (4th Ed., 1991) is Octylacrylamide / acrylates / butylaminoethylmethacrylate copolymer such as the products sold under the name AMPHOMER or LOVOCRYL 47 by the company NATIONAL STARCH.
  • R-jn represents a divalent radical derived from a saturated dicarboxylic acid, from a mono or dicarboxylic aliphatic acid with ethylene double bond, from an ester of a lower alkanol having 1 to 6 carbon atoms of these acids or of a radical derived from the addition of any one of said acids with a primary bis or secondary bis amine
  • Z denotes a radical of a bis-primary, mono or bis-secondary polyalkylene polyamine and preferably represents: a) in the proportions of 60 to 100 mol%, the radical
  • the saturated carboxylic acids are preferably chosen from acids having 6 to 10 carbon atoms such as adipic, trimethyl-2,2,4-adipic acid and trimethyl-2,4,4-adi ⁇ ique, terephthalic acid, ethylenic double bond such as for example acrylic, methacrylic, itaconic acids.
  • the alkane sultones used in the alkylation are preferably propane or butane sultone, the salts of the alkylating agents are preferably the sodium or potassium salts.
  • denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group
  • y and z represents an integer from 1 to 3
  • R ⁇ and R13 represent a hydrogen, methyl, ethyl or propyl atom
  • R14 and R15 represent a hydrogen atom or an alkyl radical such that the sum of the carbon atoms in R-
  • the polymers comprising such units may also contain units derived from non-zwitterionic monomers such as dimethyl or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates, acrylamides or methacrylamides or vinyl acetate.
  • non-zwitterionic monomers such as dimethyl or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates, acrylamides or methacrylamides or vinyl acetate.
  • non-zwitterionic monomers such as dimethyl or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates, acrylamides or methacrylamides or vinyl acetate.
  • the copolymer of methyl methacrylate / di-methyl carboxymethylammonio ethyl methacrylate such as the product sold under the name DIAFORMER Z301 by the company SANDOZ.
  • R 16 represents a radical of formula:
  • R20 represents a hydrogen atom, a CH3O radical, CH3CH2O, phenyl
  • R2 denotes hydrogen or a lower alkyl radical such as methyl, ethyl
  • R22 denotes hydrogen or a lower alkyl radical such as methyl, ethyl
  • R23 denotes a lower alkyl radical such as methyl, ethyl or a radical corresponding to the formula: -R24-N (R22) 2 >
  • R 24 representing a group -CH2-CH2-, -CH 2 -CH 2 -CH 2 -, -CH 2 -CH (CH 3 ) -, R 2 2 having the meanings mentioned above, as well as the higher homologs of these radicals and containing up to 6 carbon atoms.
  • WHERE D denotes a radical
  • ⁇ / and X denotes the symbol E or E ', E or E', which are identical or different, denote a bivalent radical which is an alkylene radical with a straight or branched chain containing up to 7 carbon atoms in the unsubstituted main chain or substituted by hydroxyl groups and which may additionally contain oxygen, nitrogen, sulfur atoms, 1 to 3 aromatic and / or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine, alkenylamine groups, hydroxyl groups, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and / or urethane.
  • E denotes the symbol E or E 'and at least once E';
  • E having the meaning indicated above and E 'is a bivalent radical which is a straight or branched chain alkylene radical having up to 7 carbon atoms in the main chain, substituted or not by one or more hydroxyl radicals and comprising as one or more nitrogen atoms, the nitrogen atom being substituted by an alkyl chain optionally interrupted by an oxygen atom and necessarily having one or more carboxyl functions or one or more hydroxyl functions and betainized by reaction with chloracetic acid or sodium chloracetate.
  • alkyl (C1-C5) vinyl ether / maleic anhydride copolymers partially modified by semiamidification with an N, N-dialkylaminoalkylamine such as N, N-dimethylaminopropylamine or by semiesterification with an N, N-dialcanolamine.
  • These copolymers can also contain other vinyl co-monomers such as vinylcaprolactam.
  • amphoteric film-forming polymers which are particularly preferred according to the invention are those of the family (3) such as the copolymers whose name CTFA is Octylacrylamide / acrylates / butylaminoethylmethacrylate copolymer such as the products sold under the names AMPHOMER, AMHOMER LV 71 or LOVOCRYL 47 by NATIONAL STARCH and those of the fa- thousand (4) such as the copolymers of methyl methacrylate / dimethyl carboxymethylammonio ethyl methyl methacrylate, for example sold under the name DIAFORMER Z301 by the company SANDOZ.
  • nonionic film-forming polymers which can be used according to the present invention are chosen, for example, from:
  • polyalkyloxazolines such as polyethyloxazoiines offered by the company DOW CHEMICAL under the names PEOX 50 000, PEOX
  • homopolymers of alkyl acrylates and homopolymers of alkyl methacrylates such as the product offered under the name MICROPEARL RQ 750 by the company MATSUMOTO or the product offered under the name LUHYDRAN A 848 S by the company BASF;
  • modified nonionic guar gums are for example the products sold under the name VIDOGUM GH 175 by the company UNIPECTINE and under the name JAGUAR C by the company MEYHALL.
  • the modified nonionic guar gums which can be used according to the invention are preferably modified with C 1 -C 6 hydroxyalkyl groups. Mention may be made, by way of example, of the hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.
  • guar gums are well known in the state of the art and can for example be prepared by reacting corresponding alkene oxides, such as for example propylene oxides, with guar gum so as to obtain a gum of guar modified by hydroxypropyl groups.
  • nonionic guar gums possibly modified with hydroxyalkyl groups are for example sold under the trade names JAGUAR HP8, JAGUAR HP60 and JAGUAR HP120, JAGUAR DC 293 and JAGUAR HP 105 by the company MEYHALL, or under the name GALACTASOL 4H4FD2 the AQUALON company.
  • the alkyl radicals of nonionic polymers have from 1 to 6 carbon atoms unless otherwise stated.
  • film-forming polymers of the grafted silicone type comprising a polysiloxane portion and a portion consisting of a non-silicone organic chain, one of the two portions constituting the main chain of the polymer the other being grafted on the said main channel.
  • These polymers are for example described in patent applications EP-A-0412 704, EP-A-0 412 707, EP-A-0 640 105 and WO 95/00578, EP-A-0582 152 and WO 93/23009 and US patents 4,693,935, US 4,728,571 and US 4,972,037.
  • These polymers are preferably anionic or nonionic.
  • Such polymers are, for example, the copolymers capable of being obtained by radical polymerization from the mixture of monomers consisting of: a) 50 to 90% by weight of tert-butyl acrylate; b) 0 to 40% by weight of acrylic acid; c) 5 to 40% by weight of silicone macromer of formula:
  • CH '2 (CH 2 ) 3 - - CH,
  • v being a number ranging from 5 to 700; the weight percentages being calculated relative to the total weight of the monomers.
  • grafted silicone polymers are in particular polydimethylsiloxanes (PDMS) onto which are grafted, via a thiopropylene-type connecting link, mixed polymer units of the poly (meth) acrylic acid type and poly (meth) acrylate type and polydimethylsiloxanes (PDMS) onto which are grafted, via a thiopropylene type connecting link, polymer units of the poly (meth) acrylate type isobutyl.
  • PDMS polydimethylsiloxanes
  • B film-forming polymers
  • the distribution means which forms part of the pump bottle device, generally consists of at least one pump operating for the suction and / or delivery of the liquid and the air. This pump is controlled by a dispensing head, itself comprising a nozzle by which the composition is vaporized.
  • a pump bottle device which delivers an amount of composition between 120 and 170 ⁇ l when the user applies 1 press on the push button, and preferably an amount of composition between 140 and 160 ⁇ l.
  • the diameter of the droplets is measured for a temperature of the composition close to 20 ° C. inside the pump bottle device.
  • the pump bottle device is placed at room temperature and the diameter of the droplets is measured at 20 cm from the nozzle.
  • the polycondensates used in accordance with the invention may be soluble in the cosmetically acceptable medium or else form a dispersion in this medium.
  • the dispersion can then comprise at least 0.05% of surfactant enabling the polycondensate to be dispersed and maintained in dispersion.
  • any type of surfactant can be used in said dispersion, but preferably a nonionic surfactant.
  • the average particle size of the polycondensate in the dispersion is preferably between 0.1 and 1 micron.
  • composition according to the invention advantageously comprises, in relative proportion by weight relative to the total weight of the composition, between 0.1 and 30% of the polycondensate (A) comprising at least one polyurethane and / or polyurea block, more advantageously between 0.5 and 20%, and even more advantageously between 1 and 10% of this polycondensate.
  • composition according to the invention advantageously comprises, in relative proportion by weight relative to the total weight of the composition, between 0.1 and 30% of the film-forming polymer (B), more advantageously between 0.5 and 20%, and again more advantageously between 1 and 10% of film-forming polymer (B).
  • It can comprise an additional organic solvent, in a proportion varying between 0.5 and 80%.
  • the organic solvent is chosen in particular from the group comprising C1 to C alcohols such as ethanol or isopropanol, acetone, methyl ethyl ketone, methyl acetate, acetate butyl, ethyl acetate, dimethoxyethane, diethoxyethane and mixtures thereof.
  • ethanol is used.
  • compositions in accordance with the invention may also contain conventional cosmetic additives chosen in particular from fatty substances, thickening agents, softeners, anti-foaming agents, moisturizing agents, antiperspirant agents, alkalizing agents, dyes, pigments, perfumes, preservatives, surfactants, polymers other than those of the invention, volatile and non-volatile silicones, in particular anionic silicones, polyols, proteins and vitamins.
  • conventional cosmetic additives chosen in particular from fatty substances, thickening agents, softeners, anti-foaming agents, moisturizing agents, antiperspirant agents, alkalizing agents, dyes, pigments, perfumes, preservatives, surfactants, polymers other than those of the invention, volatile and non-volatile silicones, in particular anionic silicones, polyols, proteins and vitamins.
  • Example The quality of the spraying obtained by means of pump bottles according to the invention is compared with that obtained with pump bottles of the prior art.
  • the three pump bottles according to the invention all contain the same composition I comprising a polyurethane and differ from each other by the distribution means.
  • the pump bottles in accordance with the prior art contain fixing compositions without polyurethane, namely Mighty Mist ® marketed by Oreai and Pantène ® marketed by Procter & Gamble.
  • the following devices are used: - Euromist 140 marketed by Seaquist and which delivers 140 ⁇ l of composition for 1 pressure exerted by the user
  • pump bottles according to the present invention provide finer droplets than the pump bottles according to the prior art.
  • the pump bottles in accordance with the invention therefore provide a more homogeneous spraying of the product on the hair than the pump bottles of the prior art.

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Abstract

The invention concerns aerosol devices comprising a reservoir containing, in a cosmetically suitable medium, a multiple-block polymer (A) comprising at least a polyurethane and/or polyurea unit and a film-forming polymer (B), the polymers (A) and (B) and the device being selected so as to obtain, at the device outlet, droplets of composition with average diameter less than 80 νm. The invention also concerns a hairstyling or hair-fixing method comprising the use of said devices and their use for making a hairstyling product.

Description

DISPOSITIF FLACON POMPE CONTENANT UN POLYCONDENSAT COMPRENANT AU MOINS UN MOTIF POLYURETHANNE ET/OU POLYUREEPUMP BOTTLE DEVICE CONTAINING A POLYCONDENSATE COMPRISING AT LEAST ONE POLYURETHANE AND / OR POLYUREA PATTERN
L'invention a pour objet des dispositifs flacons pompes comprenant un réser- vofr qui contient, dans un milieu cosmétiquement acceptable, un polymère (A) multiséquencé comprenant au moins un motif polyuréthanne et/ou polyurée et un polymère fiimogène (B), les polymères (A) et (B) et le dispositif étant choisis de sorte à obtenir, à la sortie du dispositif, des gouttelettes de composition de diamètre moyen inférieur à 80 μm. Elle vise également un procédé pour la mise en forme ou le maintien de la coiffure comprenant la mise en oeuvre de ces dispositifs ainsi que leur utilisation pour la fabrication d'un produit de coiffage.The subject of the invention is pump bottle devices comprising a reservoir which contains, in a cosmetically acceptable medium, a multiblock polymer (A) comprising at least one polyurethane and / or polyurea unit and a film-forming polymer (B), the polymers (A) and (B) and the device being chosen so as to obtain, at the outlet of the device, droplets of composition with an average diameter of less than 80 μm. It also relates to a method for shaping or maintaining the hairstyle comprising the implementation of these devices as well as their use for the manufacture of a styling product.
La fixation de la coiffure est un élément important du coiffage qui consiste à maintenir la mise en forme déjà réalisée ou à mettre en forme les cheveux et à les fixer simultanément.The fixing of the hairstyle is an important element of the styling which consists in maintaining the shaping already carried out or in shaping the hair and in fixing them simultaneously.
Les produits capillaires pour la mise en forme et/ou le maintien de la coiffure les plus répandus sur le marché de la cosmétique sont des composi- tions à pulvériser essentiellement constituées d'une solution le plus souvent alcoolique et/ou aqueuse et d'un ou plusieurs matériaux, généralement des résines polymères, dont la fonction est de former des soudures entre les cheveux/ appelés encore matériaux fixants, en mélange avec divers adjuvants cosmétiques. Cette solution peut être conditionnée par exemple dans un flacon pompe.The most widespread haircare products for shaping and / or maintaining the hairstyle on the cosmetics market are spray compositions essentially consisting of a solution, most often alcoholic and / or aqueous and of a or several materials, generally polymer resins, the function of which is to form welds between the hair / also called fixing materials, in admixture with various cosmetic adjuvants. This solution can be packaged for example in a pump bottle.
Pour satisfaire aux obligations liées à l'environnement, les compositions pour la fixation de la coiffure doivent dégager de moins en moins de composés organiques volatiles (VOC). A cet effet, la quantité de solvants organiques vo- latiles dans la composition est diminuée et ces solvants sont remplacés par de l'eau. Toutefois, cette modification de la formulation des compositions capillaires a pour effet néfaste d'augmenter fortement leur viscosité. Le conditionnement sous forme flacon pompe est spécialement pratique pour l'utilisateur qui peut facilement doser la quantité de produit qu'il souhaite appliquer. Toutefois, ce type de conditionnement rend parfois difficile l'application du produit de façon homogène sur les cheveux, car les gouttelettes de produit sortant du flacon pompe sont souvent trop grosses. Cet inconvénient est particulièrement marqué pour les compositions visqueuses pour lesquelles des gouttelettes fines sont difficilement obtenues.To meet environmental obligations, the compositions for fixing the hairstyle must release less and less volatile organic compounds (VOC). To this end, the amount of volatile organic solvents in the composition is reduced and these solvents are replaced by water. However, this modification of the formulation of the hair compositions has the harmful effect of greatly increasing their viscosity. Packaging in the form of a pump bottle is especially practical for the user, who can easily dose the quantity of product he wishes to apply. However, this type of packaging sometimes makes it difficult to apply the product evenly to the hair, since the droplets of product leaving the pump bottle are often too large. This drawback is particularly marked for viscous compositions for which fine droplets are difficult to obtain.
La qualité de la pulvérisation obtenue au moyen d'un dispositif flacon pompe, c'est-à-dire essentiellement la distribution des gouttelettes dans l'espace à la sortie de la buse, dépend fortement de la constitution chimique de la composition mise en œuvre. On porte donc un intérêt tout particulier à la réalisation de dispositifs flacons pompes qui donnent lieu à de fines gouttelettes, en dépit d'une viscosité élevée des compositions.The quality of the spraying obtained by means of a pump-bottle device, that is to say essentially the distribution of the droplets in the space at the outlet of the nozzle, strongly depends on the chemical constitution of the composition used. . There is therefore a very particular interest in the production of pump bottle devices which give rise to fine droplets, despite the high viscosity of the compositions.
Il est connu par le brevet DE 19541 326 de préparer des compositions de coiffage comprenant un polymère à motif polyuréthanne en tant que polymère fixant. Les dispositifs peuvent toutefois être améliorés en ce qui concerne notamment les propriétés cosmétiques qu'ils confèrent aux cheveux tout en of- frant une meilleure qualité de pulvérisation.It is known from patent DE 19541 326 to prepare styling compositions comprising a polymer with a polyurethane pattern as fixing polymer. The devices can however be improved as regards in particular the cosmetic properties which they confer on the hair while offering a better quality of spraying.
De manière surprenante et inattendue, la Demanderesse a découvert, contre toute attente, qu'il était possible de réaliser des dispositifs flacons pompes qui satisfont aux exigences exprimées ci-dessus, en opérant une sélection d'une part, sur la composition cosmétique et d'autre part, sur les moyens de distribution de cette composition.Surprisingly and unexpectedly, the Applicant has discovered, against all expectations, that it was possible to produce pump bottle devices which meet the requirements expressed above, by making a selection on the one hand, on the cosmetic composition and on the other. on the other hand, on the means of distribution of this composition.
L'invention a pour objet un dispositif flacon pompe comprenant un réservoir contenant une composition capillaire ainsi que des moyens de distribution de la composition, caractérisé par le fait que: (1) la composition comprend, dans un milieu cosmétiquement acceptable, au moins un polycondensat (A) comprenant au moins une séquence polyuréthanne et/ou polyurée et au moins un polymère filmogène (B) différent de (A);The subject of the invention is a pump bottle device comprising a reservoir containing a hair composition as well as means for dispensing the composition, characterized in that: (1) the composition comprises, in a cosmetically acceptable medium, at least one polycondensate (A) comprising at least one polyurethane and / or polyurea block and at least one film-forming polymer (B) different from (A);
(2) les polymères (A) et (B) et le dispositif étant choisis de sorte à obtenir, à la sortie du dispositif, des gouttelettes de composition de diamètre moyen inférieur ou égal à 80 μm.(2) the polymers (A) and (B) and the device being chosen so as to obtain, at the outlet of the device, droplets of composition with an average diameter less than or equal to 80 μm.
Un autre objet de l'invention concerne un procédé pour la mise en forme ou le maintien de la coiffure comprenant la mise en oeuvre de ce dispositif fla- con pompe.Another object of the invention relates to a method for shaping or maintaining the hairstyle comprising the use of this pump-flask device.
Encore un autre objet de l'invention concerne l'utilisation de ce dispositif pour la fabrication d'un produit de coiffage.Yet another object of the invention relates to the use of this device for the manufacture of a styling product.
Les polycondensats comprenant au moins une séquence polyuréthanne et/ou polyurée particulièrement visés par la présente invention sont ceux décrits dans les brevets EP 0 751 162, EP 0 637 600, FR 2 743 297 et EP 0 648 485 dont la Demanderesse est Titulaire, ainsi que le brevets EP 0 656 021 ou WO 94/03510 de la Société BASF et EP 0 619 111 de la Société National Starch.The polycondensates comprising at least one polyurethane and / or polyurea block which are particularly targeted by the present invention are those described in patents EP 0 751 162, EP 0 637 600, FR 2 743 297 and EP 0 648 485 of which the Applicant is the Holder, as well that EP 0 656 021 or WO 94/03510 from BASF and EP 0 619 111 from National Starch.
Les polycondensats utilisés conformément à l'invention peuvent être so- lubles dans le milieu cosmétiquement acceptable, notamment après neutralisation par une base organique ou minérale, ou encore former une dispersion dans ce milieu. La dispersion peut comprendre alors au moins 0,05 % de tensioactif permettant la mise en dispersion et le maintien en dispersion du polycondensat.The polycondensates used in accordance with the invention may be soluble in the cosmetically acceptable medium, in particular after neutralization with an organic or inorganic base, or else form a dispersion in this medium. The dispersion can then comprise at least 0.05% of surfactant enabling the polycondensate to be dispersed and maintained in dispersion.
Selon l'invention, on peut utiliser tout type de tensioactif dans ladite dis- persion, mais de préférence un tensioactif non ionique. La taille moyenne des particules du polycondensat dans la dispersion est de préférence comprise entre 0,1 et 1 micron. A titre d'exemple, le polycondensat peut être formé par un arrangement de blocs, cet arrangement étant obtenu notamment à partir de:According to the invention, any type of surfactant can be used in said dispersion, but preferably a nonionic surfactant. The average particle size of the polycondensate in the dispersion is preferably between 0.1 and 1 micron. By way of example, the polycondensate can be formed by an arrangement of blocks, this arrangement being obtained in particular from:
(1 ) au moins un composé qui contient deux ou plus de deux atomes d'hy- dro gène actifs par molécule;(1) at least one compound that contains two or more than two active hydrogen atoms per molecule;
'' (2) au moins un diol ou un mélange de diols contenant des radicaux acides ou leurs sels; '(2) at least one diol or a mixture of diols containing acid radicals or their salts;
(3) au moins un di- ou polyisocyanate.(3) at least one di- or polyisocyanate.
Avantageusement, les composés (1 ) sont choisis dans le groupe comprenant les diols, les diamiπes, les polyesterols, les polyétherols ou leur mélange.Advantageously, the compounds (1) are chosen from the group comprising diols, diamiπes, polyesterols, polyetherols or their mixture.
Les composés (1 ) qui sont préférés sont les polyéthylène et les polypro- pylène glycols linéaires, en particulier ceux qui sont obtenus par réaction de l'oxyde d'éthylène ou de propylene avec l'eau ou du diéthylène ou du dipropy- lène glycol en présence d'hydroxyde de sodium en tant que catalyseur. Ces polyglycols ont généralement un poids moléculaire compris entre environ 600 et 20000.The compounds (1) which are preferred are linear polyethylene and polypropylene glycols, in particular those obtained by reaction of ethylene or propylene oxide with water or of diethylene or dipropylene glycol in the presence of sodium hydroxide as a catalyst. These polyglycols generally have a molecular weight of between about 600 and 20,000.
D'autres composés organiques préférés sont ceux qui ont des groupes mercapto, amino, carboxyle ou hydroxyle. Parmi ceux-ci, on cite plus particulièrement les composés polyhydroxy tels que les polyéther diols, les polyester diols,- les polyacétal diols, les polyamide diols, les polyester polyamide diols, les poly(alkylène éther) diols, les polythioéther diols et les polycarbonate diols.Other preferred organic compounds are those which have mercapto, amino, carboxyl or hydroxyl groups. Among these, there are more particularly polyhydroxy compounds such as polyether diols, polyester diols, - polyacetal diols, polyamide diols, polyester polyamide diols, poly (alkylene ether) diols, polythioether diols and polycarbonate diols.
Les polyéther diols préférés sont, par exemple, les produits de condensation d'oxyde d'éthylène, d'oxyde de propylene ou de tétrahydrofurane, leurs produits de copolymérisation ou de condensation, greffés ou blocs, tels que les mélanges de condensats d'oxyde d'éthylène et de propylene, et les produits de polymérisation d'oléfines, sous haute pression, avec les condensats d'oxyde d'alkylène. Des polyéthers appropriés sont par exemple préparés par conden- sation d'oxydes d'alkylène et d'alcools polyhydriques, tels que l'éthylène glycol, le 1 ,2-propylène glycol et le 1 ,4-butanediol.The preferred polyether diols are, for example, the condensation products of ethylene oxide, propylene oxide or tetrahydrofuran, their copolymerization or condensation products, grafted or block, such as mixtures of oxide condensates ethylene and propylene, and the polymerization of olefins, under high pressure, with alkylene oxide condensates. Suitable polyethers are for example prepared by conden- sation of alkylene oxides and polyhydric alcohols, such as ethylene glycol, 1,2-propylene glycol and 1,4-butanediol.
Les polyesters diols, polyesters amides, polyamides diols sont de préfé- rence saturés et sont obtenus, par exemple, à partir de la réaction d'acides pofycarboxyliques saturés ou insaturés avec des alcools polyhydriques, des diamines ou des polyamines. Pour préparer ces composés, on peut utiliser, par exemple, l'acide adipique, l'acide succinique, l'acide phtalique, l'acide téréph- talique et l'acide maléique. Des alcools polyhydriques appropriés pour préparer les polyesters incluent par exemple l'éthylène glycol, le 1 ,2-propylène glycol, le 1 ,4-butanediol, le néopentyl glycol et l'hexane diol. On peut aussi utiliser des aminoalcools, par exemple l'éthanolamiπe. Des diamines appropriés pour préparer les amides polyesters sont l'éthylène diamine et l'hexaméthylène dia- mine.The polyester diols, polyester amides and polyamide diols are preferably saturated and are obtained, for example, from the reaction of saturated or unsaturated pofycarboxylic acids with polyhydric alcohols, diamines or polyamines. To prepare these compounds, one can use, for example, adipic acid, succinic acid, phthalic acid, terephthalic acid and maleic acid. Polyhydric alcohols suitable for preparing polyesters include, for example, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, neopentyl glycol and hexane diol. One can also use amino alcohols, for example ethanolamiπe. Diamines suitable for preparing polyester amides are ethylene diamine and hexamethylene diamine.
Des polyacétals appropriés peuvent être préparés, par exemple, à partir de 1 ,4-butanediol ou d'hexanediol et de formaldéhyde. Des polythioéthers appropriés peuvent être préparés par exemple par réaction de condensation entre des thioglycol soit seuls ou en combinaison avec d'autres glycols tels que l'éthylène glycol, le 1 ,2-propylène glycol ou avec d'autres composés polyhy- droxylés. Les composés polyhydroxylés contenant déjà des groupements urée ou uréthanne, des polyols naturels, qui peuvent être davantage modifiés, par exemple, l'huile de castor et les carbohydrates peuvent également être utilisés.Suitable polyacetals can be prepared, for example, from 1,4-butanediol or hexanediol and formaldehyde. Suitable polythioethers can be prepared, for example, by condensation reaction between thioglycols either alone or in combination with other glycols such as ethylene glycol, 1,2-propylene glycol or with other polyhydroxy compounds. Polyhydroxy compounds already containing urea or urethane groups, natural polyols, which can be further modified, for example, beaver oil and carbohydrates can also be used.
Plus préférentiellement, le composé du groupe (1) est un polyestérol, notamment un polyester diol formé par la réaction d'au moins un (di)-polyol (1a) et d'au moins un acide (1b). Le (di)- polyol (1a) est en particulier choisi dans le groupe comprenant le πéopentylglycol, le butanediol-1,4, l'hexanediol, l'éthylè- neglycol, le diéthylène glycol, le propylèneglycol, le butylèneglycol, le néopen- tyiglycol et (di)-polyéthylèneglycol. L'acide (1b) est en particulier choisi dans le groupe comprenant l'acide phtalique, l'acide isophtalique, l'acide adipique et l'acide (poly)-lactique. En tant que composé (2), on peut notamment utiliser un acide hydroxy- carboxylique tel que l'acide diméthylol propanoïque (DMPA) ou un acide car- boxylique 2,2-hydroxyméthyl. En général, le composé (2) est utile en tant que bloc de couplage. En tant que composés (2), on préfère ceux comprenant au moins un poly (acide-(alpha-hydroxycarboxyliquediol)).More preferably, the compound of group (1) is a polyesterol, in particular a polyester diol formed by the reaction of at least one (di) -polyol (1 a ) and at least one acid (1 b ). The (di) - polyol (1 a ) is in particular chosen from the group comprising πéopentylglycol, 1,4-butanediol, hexanediol, ethylene-glycol, diethylene glycol, propylene glycol, butylene glycol, neopen - tyiglycol and (di) -polyethylene glycol. The acid ( 1b ) is in particular chosen from the group comprising phthalic acid, isophthalic acid, adipic acid and (poly) -lactic acid. As compound (2), it is possible in particular to use a hydroxycarboxylic acid such as dimethylol propanoic acid (DMPA) or a carboxylic acid 2,2-hydroxymethyl. In general, compound (2) is useful as a coupling block. As compounds (2), preferred are those comprising at least one poly (acid- (alpha-hydroxycarboxyliquediol)).
Les composés (2) particulièrement préférés conformément à l'invention sont ceux choisis dans le groupe comprenant le 2,2-di-(hydroxyméthyl) acide acétique, le 2,2-dihydroxyméthyl acide propionique, le 2,2-dihydroxyméthyl acide butyrique, l'acide 2,2-dihydroxyméthyl acide pentanoïque.The compounds (2) which are particularly preferred in accordance with the invention are those chosen from the group comprising 2,2-di- (hydroxymethyl) acetic acid, 2,2-dihydroxymethyl propionic acid, 2,2-dihydroxymethyl butyric acid, 2,2-dihydroxymethyl pentanoic acid.
Le di- ou polyisocyanate (3) peut être choisi en particulier dans le groupe comprenant l'hexaméthylène diisocyanate, l'isophorondiisocyanate (IDPI), le toluylendiisocyanate, le diphénylméthane 4,4'-diisocyanate (DPMD) et le dicy- clohexylméthane 4,4'-diisocyanate (DCMD), le méthylène-di-p-phényl diisocyanate, le méthylène-bis(4-cyclohexylisocyanate), l'isophorone diisocyanate, le toluène diisocyanate, le 1 ,5-naphtalène diisocyanate, le 4,4' -diphénylméthane diisocyanate, le 2,2'-diméthyl-4,4'-diphénylméthane diisocyanate, le 1 ,3- phénylene diisocyanate, le 1 ,4-phénylène diisocyanate, des mélanges de 2,4- et de 2,6- toluène diisocyanate, le 2,2'-dichioro-4,4'-diisocyanato diphénylméthane, Ie 2,4-dibromo-1 ,5-diisocyanato naphtalène, le 1 ,4-diisocyanate butane, l'hexane-1 ,6-diisocyanate, le cyclohexane-1 ,4-diisocyanate.The di- or polyisocyanate (3) can be chosen in particular from the group comprising hexamethylene diisocyanate, isophorondiisocyanate (IDPI), toluylendiisocyanate, diphenylmethane 4,4'-diisocyanate (DPMD) and dicy-clohexylmethane 4, 4'-diisocyanate (DCMD), methylene-di-p-phenyl diisocyanate, methylene-bis (4-cyclohexylisocyanate), isophorone diisocyanate, toluene diisocyanate, 1,5-naphthalene diisocyanate, 4,4 ' -diphenylmethane diisocyanate, 2,2'-dimethyl-4,4'-diphenylmethane diisocyanate, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, 2,2'-dichioro-4,4'-diisocyanato diphenylmethane, Ie 2,4-dibromo-1, 5-diisocyanato naphthalene, 1, 4-diisocyanate butane, hexane-1, 6-diisocyanate, cyclohexane-1,4-diisocyanate.
Le polycondensat peut être formé à l'aide d'un composé supplémentaireThe polycondensate can be formed using an additional compound
(4) servant en général à allonger la chaîne du polycondensat. Ces composés (4) peuvent être choisis dans la groupe comprenant notamment les glycols saturés ou insaturés tel que l'éthylène glycol, le diéthylène glycol, le néopentyl- glycol, le triéthylène glycol, les aminoalcools tels que l'éthanolamine, la propa- noiamine, la butanolamine, les aminés primaires hétérocyclique, aromatique, cycloaliphatique, et aliphatique, les diamines, les acides carboxyiique tels que les acides carboxyliques aliphatique, aromatique, hétérocyclique comme l'acide oxalique, succinique, glutarique, adipique, sébacique, téréphtalique, les acides aminocarboxyliques. Les composés (4) préférés sont les diols aliphatiques.(4) generally used to lengthen the chain of the polycondensate. These compounds (4) can be chosen from the group comprising in particular saturated or unsaturated glycols such as ethylene glycol, diethylene glycol, neopentyl glycol, triethylene glycol, amino alcohols such as ethanolamine, propanoinamine , butanolamine, primary heterocyclic, aromatic, cycloaliphatic, and aliphatic amines, diamines, carboxyic acids such as aliphatic, aromatic, heterocyclic carboxylic acids such as acid oxalic, succinic, glutaric, adipic, sebacic, terephthalic, aminocarboxylic acids. The preferred compounds (4) are the aliphatic diols.
Les polycondensats conformes à l'invention peuvent également être for- mes à partir de composés supplémentaires (5) ayant un squelette silicone tels que les polysiloxanes, les polyalkylsiloxanes ou les polyarylsiloxanes notamment les polyéthylsiloxanes, les polyméthylsiloxanes et les polyphénylsiloxa- nes, comportant éventuellement des chaînes hydrocarbonées greffées sur les atomes de silicium.The polycondensates in accordance with the invention can also be formed from additional compounds (5) having a silicone skeleton such as polysiloxanes, polyalkylsiloxanes or polyarylsiloxanes, in particular polyethylsiloxanes, polymethylsiloxanes and polyphenylsiloxanes, optionally comprising hydrocarbon chains grafted onto silicon atoms.
Les séquences de polyuréthanne et/ou polyurée du polymère utilisées avantageusement présentent un motif répétitif de base répondant à la formule générale ci-après:The polyurethane and / or polyurea blocks of the polymer advantageously used have a basic repeating unit corresponding to the general formula below:
- X' - B - X' - CO - NH - R - NH - CO - (I')- X '- B - X' - CO - NH - R - NH - CO - (I ')
dans laquelle :in which :
- X' représente 0 et/ou NH, - B est un radical hydrocarboné bivalent, ce radical étant substitué ou non, et- X 'represents 0 and / or NH, - B is a bivalent hydrocarbon radical, this radical being substituted or not, and
- R est un radical divalent choisi parmi les radicaux alkylène de type aromatique, aliphatique en Ci à C2o, cycloaliphatique en Ci à C20, ces radicaux étant substitués ou non.- R is a divalent radical chosen from alkylene radicals of aromatic type, aliphatic C l -C 2 o cycloaliphatic Ci -C 20, these radicals being substituted or unsubstituted.
De préférence, le radical B est un radical en Ci à C30 et est porteur d'un groupement présentant une ou des fonction(s) carboxylique(s) et/ou une ou des fonctions sulfoniques, lesdites fonctions carboxyliques et/ou sulfoniques étant sous forme libre ou bien neutralisées partiellement ou totalement par une base minérale ou organique. Le radical R est avantageusement choisi parmi les radicaux répondant aux formules suivantes:Preferably, the radical B is a C 1 to C 30 radical and carries a group having one or more carboxylic function (s) and / or one or more sulfonic functions, said carboxylic and / or sulfonic functions being in free form or partially or totally neutralized with a mineral or organic base. The radical R is advantageously chosen from the radicals corresponding to the following formulas:
Figure imgf000010_0001
Figure imgf000010_0001
Figure imgf000010_0002
Figure imgf000010_0002
Figure imgf000010_0003
Figure imgf000010_0003
Figure imgf000010_0004
Figure imgf000010_0004
dans lesquelles b est un nombre entier compris entre 0 et 3, et c un nombre entier compris entre 1 et 20, de préférence compris entre 2 et 12.in which b is an integer between 0 and 3, and c is an integer between 1 and 20, preferably between 2 and 12.
En particulier, le radical R est choisi parmi les radicaux hexaméthylène,In particular, the radical R is chosen from hexamethylene radicals,
4,4'-biphénylèneméthane, 2,4- et/ou 2,6-tolylèπe, 1 ,5-naphtylène, p-phénylène, méthylène- 4,4bis - cyclohexyle et le radical divalent dérivé de l'isophorone.4,4'-biphenylenemethane, 2,4- and / or 2,6-tolylèπe, 1,5-naphthylene, p-phenylene, methylene- 4,4bis - cyclohexyl and the divalent radical derived from isophorone.
Le polycondensat mis en œuvre conformément à l'invention comprenant au moins une séquence polyuréthanne et/ou polyurée peut avantageusement comprendre en outre au moins une séquence polysiloxane dont le motif répétitif de base répond par exemple à la formule générale (II') ci-après:The polycondensate used according to the invention comprising at least one polyurethane and / or polyurea block can advantageously further comprise at least one polysiloxane block whose basic repeating unit corresponds for example to the general formula (II ′) below :
- X* - P - X' - CO - NH - R - NH - CO - (II')- X * - P - X '- CO - NH - R - NH - CO - (II')
dans laquelle :in which :
- P est un segment polysiloxanique,- P is a polysiloxane segment,
- X' représente O et/ou NH, et - R est un radical divalent choisi parmi les radicaux alkylènes de type aromatique, aliphatique en Ci à C20, cycloaliphatique en d à C20, ces radicaux étant substitués ou non.- X 'represents O and / or NH, and - R is a divalent radical chosen from alkylene radicals of aromatic, aliphatic C 1 -C 20 , cycloaliphatic C 1 to C 20 type , these radicals being substituted or unsubstituted.
Avantageusement, le segment polysiloxanique P répond à la formule générale ci-après:Advantageously, the polysiloxane segment P corresponds to the general formula below:
A AA A
I II I
- Y - (Si - O )z - Si - Y- ( III )- Y - (Si - O) z - Si - Y- (III)
I II I
A AA A
dans laquelle: - les radicaux A, qui peuvent être identiques ou différents, sont choisis parmi d'une part les radicaux hydrocarbonés monovalents en d à C20 exempts ou substantiellement exempts d'insaturation éthylénique et, d'autre part, les radicaux aromatiques, - Y représente un radical hydrocarboné bivalent, et - z représente un nombre entier, choisi de telle sorte que le poids moléculaire moyen du segment polysiloxane soit compris entre 300 et 10 000.in which: the radicals A, which may be identical or different, are chosen from on the one hand the monovalent hydrocarbon radicals in d to C 20 free or substantially free of ethylenic unsaturation and, on the other hand, the aromatic radicals, - Y represents a bivalent hydrocarbon radical, and - z represents an integer, chosen such that the average molecular weight of the polysiloxane segment is between 300 and 10,000.
En général, le radical bivalent Y est choisi parmi les radicaux alkylène de formule -(CH2)a- , dans laquelle a représente un nombre entier pouvant être compris entre 1 et 10.In general, the bivalent radical Y is chosen from alkylene radicals of formula - (CH 2 ) a -, in which a represents an integer which can be between 1 and 10.
Les radicaux A peuvent être choisis parmi les radicaux alkyles, en particulier les radicaux méthyle, éthyle, propyle, isopropyle, butyle, pentyle, hexyle, octyle, décyle, dodecyle et octadecyle, les radicaux cycloalkyle, en particulier le radical cyclohexyle, les radicaux aryle, notamment phényle et naphtyle, les radicaux arylalkyle, notamment benzyle et phényléthyle, ainsi que les radicaux tolyle et xylyle. Les polymères filmogènes (B) cationiques, anioniques, amphotères et non ioniques utilisables conformément à l'invention sont décrits ci-après.The radicals A can be chosen from alkyl radicals, in particular methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl and octadecyl radicals, cycloalkyl radicals, in particular cyclohexyl radical, aryl radicals , in particular phenyl and naphthyl, the arylalkyl radicals, in particular benzyl and phenylethyl, as well as the tolyl and xylyl radicals. The cationic, anionic, amphoteric and nonionic film-forming polymers (B) which can be used in accordance with the invention are described below.
Les polymères filmogènes cationiques utilisables selon la présente invention sont de préférence choisis parmi les polymères comportant des groupements aminé primaire, secondaire, tertiaire et/ou quaternaire faisant partie de la chaîne polymère ou directement reliés à celle-ci, et ayant un poids moléculaire compris entre 500 et environ 5.000.000 et de préférence entre 1000 et 3.000.000.The cationic film-forming polymers which can be used according to the present invention are preferably chosen from polymers comprising primary, secondary, tertiary and / or quaternary amine groups forming part of the polymer chain or directly linked to it, and having a molecular weight of between 500 and around 5,000,000 and preferably between 1,000 and 3,000,000.
Parmi ces polymères, on peut citer plus particulièrement les polymères cationiques suivants:Among these polymers, there may be mentioned more particularly the following cationic polymers:
(1) les homopolymères ou copolymères dérivés d'esters ou d'amides acryliques ou methacryliques et comportant au moins un des motifs de formules suivantes:(1) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units of the following formulas:
--
Figure imgf000012_0001
Figure imgf000012_0001
dans lesquelles: R3 désigne un atome d'hydrogène ou un radical CH3;in which: R3 denotes a hydrogen atom or a CH3 radical;
A est un groupe alkyle linéaire ou ramifié de 1 à 6 atomes de carbone ou un groupe hydroxyalkyle de 1 à 4 atomes de carbone ;A is a linear or branched alkyl group of 1 to 6 carbon atoms or a hydroxyalkyl group of 1 to 4 carbon atoms;
R4. R5. Rβi identiques ou différents, représentent un groupe alkyle ayant de 1 à 18 atomes de carbone ou un radical benzyle; R-l et R2 représentent hydrogène ou un groupe alkyle ayant de 1 à 6 atomes de carbone;R4. R5. Rβi, identical or different, represent an alkyl group having from 1 to 18 carbon atoms or a benzyl radical; Rl and R2 represent hydrogen or an alkyl group having from 1 to 6 carbon atoms;
X désigne un anion méthosulfate ou un halogénure tel que chlorure ou bromure.X denotes a methosulfate anion or a halide such as chloride or bromide.
Les copolymères de la famille (1 ) contiennent en outre un ou plusieurs motifs dérivant de comonomères pouvant être choisis dans la famille des acrylamides, méthacrylamides, diacétones acrylamides, acrylamides et méthacrylamides substitués sur l'azote par des alkyles inférieurs, des acides acryliques ou mé- thacryiiques ou leurs esters, des vinyllactames tels que la vinyipyrroiidone ou le vinylcaprolactame, des esters vinyliques.The copolymers of family (1) also contain one or more units deriving from comonomers which can be chosen from the family of acrylamides, methacrylamides, diacetones, acrylamides, acrylamides and methacrylamides substituted on nitrogen by lower alkyls, acrylic acids or mixed - thacryic or their esters, vinyllactams such as vinyipyrroiidone or vinylcaprolactam, vinyl esters.
Ainsi, parmi ces copolymères de la famille (1 ), on peut citer :Thus, among these copolymers of family (1), there may be mentioned:
- les copolymères d'acrylamide et de diméthylaminoéthyl méthacrylate quater- nisé au sulfate de diméthyle ou avec un halogénure de diméthyle tels que celui vendu sous la dénomination HERCOFLOC par la société HERCULES,- copolymers of acrylamide and of dimethylaminoethyl methacrylate quaterized with dimethyl sulphate or with a dimethyl halide such as that sold under the name HERCOFLOC by the company HERCULES,
- les copolymères d'acrylamide et de chlorure de méthacryloyloxyéthyltriméthyl- ammonium décrit par exemple dans la demande de brevet EP-A-080976 et vendus sous la dénomination BINA QUAT P 100 par la société CIBA GEIGY, - le copolymère d'acrylamide et de méthosulfate de méthacryloyloxyéthyl- triméthylammonium vendu sous la dénomination RETEN par la société HERCULES,- the copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride described for example in patent application EP-A-080976 and sold under the name BINA QUAT P 100 by the company CIBA GEIGY, - the copolymer of acrylamide and methosulfate methacryloyloxyethyltrimethylammonium sold under the name RETEN by the company HERCULES,
- les copolymères vinyipyrroiidone / acrylate ou méthacrylate de dialkylami- noalkyle quatemisés ou non, tels que les produits vendus sous la dénomina- tion "GAFQUAT" par la société ISP comme par exemple "GAFQUAT 734" ou ""GAFQUAT 755" ou bien les produits dénommés "COPOLYMER -845, 958 et 937". Ces polymères sont décrits en détail dans les brevets français 2.077.143 et 2.393.573,- vinyipyrroiidone / acrylate or methacrylate of dialkylamino-noalkyl, quaternized or not, such as the products sold under the name "GAFQUAT" by the company ISP, for example "GAFQUAT 734" or " " GAFQUAT 755 "or the products called "COPOLYMER -845, 958 and 937". These polymers are described in detail in French patents 2,077,143 and 2,393,573,
- les terpolymères méthacrylate de diméthyl amino éthyle/ vinylcaprolactame/ vinyipyrroiidone tel que le produit vendu sous la dénomination GAFFIX VC 713 par la société ISP, - et le copolymère vinyipyrroiidone / méthacrylamide de diméthylaminopropyle quatemisé tel que le produit vendu sous la dénomination "GAFQUAT HS 100" par la société ISP.- dimethyl amino ethyl methacrylate / vinylcaprolactam / vinyipyrroiidone terpolymers such as the product sold under the name GAFFIX VC 713 by the company ISP, - And the vinyipyrroiidone / methacrylamide dimethylaminopropyl quaternized copolymer such as the product sold under the name "GAFQUAT HS 100" by the company ISP.
(2) les poiysaccharides quatemisés décrits plus particulièrement dans les brevets américains 3.589.578 et 4.031.307 tel que les gommes de guar contenant des groupements cationiques trialkylammonium.(2) the quaternized poiysaccharides described more particularly in US patents 3,589,578 and 4,031,307 such as guar gums containing cationic trialkylammonium groups.
De tels produits sont commercialisés notamment sous les dénominations commerciales de JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 par la société MEYHALLSuch products are marketed in particular under the trade names of JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 by the company MEYHALL
(3) les copolymères quaternaires de vinyipyrroiidone et de vinylimidazole tels que les produits commercialisés par BASF sous l'appellation Luviquat TFC;(3) quaternary copolymers of vinyipyrroiidone and vinylimidazole such as the products sold by BASF under the name Luviquat TFC;
(4) les chitosanes ou leurs sels; les sels utilisables sont en particulier les acétate, lactate, glutamate, gluconate ou le pyrrolidone carboxylate de chitosane .(4) chitosans or their salts; the salts which can be used are in particular the acetate, lactate, glutamate, gluconate or the pyrrolidone carboxylate of chitosan.
Parmi ces composés, on peut citer le chitosane ayant un taux de désacétyla- tion de 90,5% en poids vendu sous la dénomination KYTAN BRUT STANDARD par la société ABER TECHNOLOGIES, le pyrrolidone carboxylate de chitosane vendu sous la dénomination KYTAMER PC par la société AMERCHOL .Among these compounds, there may be mentioned chitosan having a deacetylation rate of 90.5% by weight sold under the name KYTAN BRUT STANDARD by the company ABER TECHNOLOGIES, the chitosan pyrrolidone carboxylate sold under the name KYTAMER PC by the company AMERCHOL.
(5) les dérivés de cellulose cationiques tels que les copolymères de cellulose ou de dérivés de cellulose greffés avec un monomère hydrosoluble comportant un ammonium quaternaire, et décrits notamment dans le brevet US 4 131 576, tels que les hydroxyalkyl celluloses, comme les hydroxyméthyl-, hy- droxyéthyl- ou hydroxypropyl celluloses greffées notamment avec un sel de méthacryloyloxyéthyl triméthylammonium, de méthacryiamidopropyl triméthy- lammonium, de diméthyl-diallylammonium. Les produits commercialisés répondant à cette définition sont plus particulièrement les produits vendus sous la dénomination "CELQUAT L 200" et "CELQUAT H 100" par la Société National Starch.(5) cationic cellulose derivatives such as copolymers of cellulose or of cellulose derivatives grafted with a water-soluble monomer comprising a quaternary ammonium, and described in particular in US Pat. No. 4,131,576, such as hydroxyalkyl celluloses, such as hydroxymethyl- , hydroxyethyl- or hydroxypropyl celluloses grafted in particular with a salt of methacryloyloxyethyl trimethylammonium, methacryiamidopropyl trimethylammonium, dimethyl-diallylammonium. The marketed products meeting this definition are more particularly the products sold under the name "CELQUAT L 200" and "CELQUAT H 100" by the National Starch Company.
Les polymères filmogènes anioniques généralement utilisés sont des polymères comportant des groupements dérivés d'acide carboxylique, sulforiique ou phosphorique et ont un poids moléculaire compris entre environ 500 et 5.000.000.Anionic film-forming polymers generally used are polymers containing groups derived carboxylic acid, sulforiique or phosphoric acid and have a molecular weight between about 500 and 5,000,000.
1) Les groupements carboxyliques sont apportés par des monomères mono ou diacides carboxyliques insaturés tels que ceux répondant à la formule :1) The carboxylic groups are provided by mono or unsaturated dicarboxylic acid monomers such as those corresponding to the formula:
Figure imgf000015_0001
Figure imgf000015_0001
dans laquelle n est un nombre entier de 0 à 10, Ai désigne un groupement méthylène, éventuellement relié à l'atome de carbone du groupement insaturé ou au groupement méthylène voisin lorsque n est supérieur à 1 par l'intermédiaire d'un hétéroatome tel que oxygène ou soufre, R7 désigne un atome d'hydrogène, un groupement phényle ou benzyle, Rβ désigne un atome d'hydrogène, un groupement alkyle inférieur ou carboxyle, Rg désigne un atome d'hy- drogène, un groupement alkyle inférieur, un groupement -CH2-COOH, phényle ou benzyle ;in which n is an integer from 0 to 10, Ai denotes a methylene group, optionally linked to the carbon atom of the unsaturated group or to the neighboring methylene group when n is greater than 1 via a heteroatom such as oxygen or sulfur, R7 denotes a hydrogen atom, a phenyl or benzyl group, R β denotes a hydrogen atom, a lower alkyl or carboxyl group, Rg denotes a hydrogen atom, a lower alkyl group, a -CH2-COOH group, phenyl or benzyl;
Dans la formule précitée un radical alkyle inférieur désigne de préférence un groupement ayant 1 à 4 atomes de carbone et en particulier, méthyle et éthyle.In the above formula a lower alkyl radical preferably denotes a group having 1 to 4 carbon atoms and in particular, methyl and ethyl.
Les polymères filmogènes anioniques à groupements carboxyliques préférés selon l'invention sont :The anionic film-forming polymers with carboxylic groups preferred according to the invention are:
A) Les homo- ou copolymères d'acide acrylique ou méthacrylique ou leurs sels et en particulier les produits vendus sous les dénominations VERSICOL E ou K par la société ALLIED COLLOID et ULTRAHOLD par la société BASF. Les co- polymères d'acide acrylique et d'acrylamide vendus sous la forme de leur sel de sodium sous les dénominations RETEN 421 , 423 ou 425 par la Société HERCULES, les sels de sodium des acides polyhydroxycarboxyliques.A) Homo- or copolymers of acrylic or methacrylic acid or their salts and in particular the products sold under the names VERSICOL E or K by the company ALLIED COLLOID and ULTRAHOLD by the company BASF. The co- polymers of acrylic acid and acrylamide sold in the form of their sodium salt under the names RETEN 421, 423 or 425 by the company HERCULES, the sodium salts of polyhydroxycarboxylic acids.
B) Les copolymères des acides acrylique ou méthacrylique avec un monomère monoéthylénique tel que l'éthylène, le styrène, les esters vinyliques, les esters d'acide acrylique ou méthacrylique, éventuellement greffés sur un polyalkylène glycol tel que le polyéthylène glycol et éventuellement réticulés. De tels polymères sont décrits en particulier dans le brevet français 1.222.944 et la demande allemande 2.330.956, les copolymères de ce type comportant dans leur chaîne un motif acrylamide éventuellement N-alkylé et/ou hydroxyalkylé tels que décrits notamment dans les demandes de brevets luxembourgeois 75370 et 75371 ou proposés sous la dénomination QUADRAMER par la Société AMERICAN CYANAMID. On peut également citer les copolymères d'acide acrylique et de méthacrylate d'alkyle en C1 -C et les terpolymères de vinylpyr- rolidone, d'acide acrylique et de méthacrylate d'alkyle en C1-C20 par exemple de lauryle tel que celui vendu par la société ISP sous la dénomination ACRYLIDONE LM et les terpolymères acide méthacrylique/ acrylate d'éthyle/ acrylate de tertiobutyle tel que le produit vendu sous la dénomination LUVIMER 100 P par la société BASF.B) Copolymers of acrylic or methacrylic acids with a monoethylenic monomer such as ethylene, styrene, vinyl esters, acrylic or methacrylic acid esters, optionally grafted onto a polyalkylene glycol such as polyethylene glycol and optionally crosslinked. Such polymers are described in particular in French patent 1,222,944 and German application 2,330,956, copolymers of this type comprising in their chain an acrylamide unit optionally N-alkylated and / or hydroxyalkylated as described in particular in the applications for Luxembourg patents 75370 and 75371 or offered under the name QUADRAMER by the company AMERICAN CYANAMID. Mention may also be made of copolymers of acrylic acid and of C1 -C alkyl alkyl methacrylate and of terpolymers of vinyl pyrrolidone, of acrylic acid and of C1-C20 alkyl methacrylate, for example of lauryl, such as that sold. by the company ISP under the name ACRYLIDONE LM and the methacrylic acid / ethyl acrylate / tert-butyl acrylate terpolymers such as the product sold under the name LUVIMER 100 P by the company BASF.
C) les copolymères dérivés d'acide crotonique tels que ceux comportant dans leur chaîne des motifs acétate ou propionate de vinyle et éventuellement d'autres monomères tels que esters allylique ou méthallylique, éther vinylique ou ester vinylique d'un acide carboxylique saturé linéaire ou ramifié à longue chaîne hydrocarbonée tels que ceux comportant au moins 5 atomes de car- bone, ces polymères pouvant éventuellement être greffés et réticulés ou encore un ester vinylique, allylique ou méthallylique d'un acide carboxylique - ou β-cyclique. De tels polymères sont décrits entre autres dans les brevets français 1.222.944, 1.580.545, 2.265.782, 2.265.781 , 1.564.110 et 2.439.798. Des produits commerciaux entrant dans cette classe sont les résines 28-29-30, 26- 13-14 et 28-13-10 vendues par la société NATIONAL STARCH. D) les copolymères dérivés d'acides ou d'anhydrides carboxyliques monoinsa- turés en C4-Cβ choisis parmi :C) copolymers derived from crotonic acid such as those comprising in their chain vinyl acetate or propionate units and optionally other monomers such as allyl or methallyl esters, vinyl ether or vinyl ester of a linear or branched saturated carboxylic acid with a long hydrocarbon chain such as those containing at least 5 carbon atoms, these polymers possibly being grafted and crosslinked or else a vinyl, allyl or methallyl ester of a carboxylic - or β-cyclic acid. Such polymers are described inter alia in French patents 1,222,944, 1,580,545, 2,265,782, 2,265,781, 1,564,110 and 2,439,798. Commercial products falling into this class are resins 28-29-30, 26-13-14 and 28-13-10 sold by the company NATIONAL STARCH. D) copolymers derived from C 4 -Cβ monounsaturated carboxylic acids or anhydrides chosen from:
- les copolymères comprenant (i) un ou plusieurs acides ou anhydrides maléi- que, fumarique, itaconique et (ii) au moins un monomère choisis parmi les es- ters vinyliques, les éthers vinyliques, les halogénures vinyliques, les dérivés phényivinyliques, l'acide acrylique et ses esters, les fonctions anhydrides de ces copolymères étant éventuellement monoestérifiées ou monoamidifiées. ; De tels polymères sont décrits en particulier dans les brevets US 2.047.398, 2.723.248, 2.102.113, le brevet GB 839.805 et notamment ceux vendus sous les dénominations GANTREZ AN ou ES par la société ISP.- the copolymers comprising (i) one or more maleic, fumaric, itaconic acids or anhydrides and (ii) at least one monomer chosen from vinyl esters, vinyl ethers, vinyl halides, phenyivinyl derivatives, acrylic acid and its esters, the anhydride functions of these copolymers being optionally monoesterified or monoamidified. ; Such polymers are described in particular in US patents 2,047,398, 2,723,248, 2,102,113, GB patent 839,805 and in particular those sold under the names GANTREZ AN or ES by the company ISP.
- les copolymères comprenant (i) un ou plusieurs anhydrides maléique, citra- conique, itaconique et (ii) un ou plusieurs monomères choisis parmi les esters allyliques ou méthallyliques comportant éventuellement un ou plusieurs grou- pements acrylamide, methacrylamide, α-oléfine, esters acryliques ou methacryliques, acides acrylique ou méthacrylique ou vinyipyrroiidone dans leur chaîne, les fonctions anhydrides de ces copolymères étant éventuellement monoestérifiées ou monoamidifiées. Ces polymères sont par exemple décrits dans les brevets français 2.350.384 et 2.357.241 de la demanderesse.- the copolymers comprising (i) one or more maleic, citric, itaconic anhydrides and (ii) one or more monomers chosen from allyl or methallyl esters optionally comprising one or more acrylamide, methacrylamide, α-olefin groups, esters acrylic or methacrylic, acrylic or methacrylic or vinyipyrroiidone acids in their chain, the anhydride functions of these copolymers being optionally monoesterified or monoamidified. These polymers are for example described in French patents 2,350,384 and 2,357,241 of the applicant.
E) les polyacrylamides comportant des groupements carboxylates.E) polyacrylamides containing carboxylate groups.
Les polymères comprenant les groupements sulfoniques sont des polymères comportant des motifs vinylsulfonique, styrène suifonique, naphtalène sulfoni- que ou acrylamido alkylsulfonique.The polymers comprising the sulphonic groups are polymers comprising vinyl sulphonic, sulphonic styrene, sulphonic naphthalene or alkyl sulphonic acrylamido units.
Ces polymères peuvent être notamment choisis parmi :These polymers can in particular be chosen from:
- les sels de l'acide polyvinylsulfonique ayant un poids moléculaire compris entre environ 1.000 et 100.000 ainsi que les copolymères avec un comonomère insaturé tel que les acides acrylique ou méthacrylique et leurs esters ainsi que l'acrylamide ou ses dérivés, les éthers vinyliques et la vinyipyrroiidone.- the salts of polyvinylsulfonic acid having a molecular weight of between approximately 1,000 and 100,000 as well as the copolymers with a comonomer unsaturated such as acrylic or methacrylic acids and their esters as well as acrylamide or its derivatives, vinyl ethers and vinyipyrroiidone.
- les sels de l'acide polystyrène sulfonique les sels de sodium ayant un poids moléculaire d'environ 500.000 et d'environ 100.000 vendus respectivement sous les dénominations Flexan 500 et Flexan 130 par National Starch. Ces composés sont décrits dans le brevet FR 2.198.719.the salts of polystyrene sulfonic acid the sodium salts having a molecular weight of approximately 500,000 and approximately 100,000 sold respectively under the names Flexan 500 and Flexan 130 by National Starch. These compounds are described in patent FR 2,198,719.
- les sels d'acides polyacrylamide sulfoniques ceux mentionnés dans le brevet US 4.128.631 et plus particulièrement l'acide polyacrylamidoéthylpropane sulfonique vendu sous la dénomination COSMEDIA POLYMER HSP 1180 par Henkel.- The salts of polyacrylamide sulfonic acids those mentioned in US Pat. No. 4,128,631 and more particularly polyacrylamidoethylpropane sulfonic acid sold under the name COSMEDIA POLYMER HSP 1180 by Henkel.
Selon l'invention, les polymères filmogènes anioniques sont de préférence choisis parmi les copolymères d'acide acrylique tels que le terpolymère acide acrylique / acrylate d'éthyle / N-tertiobutylacrylamide vendu sous la dénomination ULTRAHOLD STRONG par la société BASF, les copolymères dérivés d'acide crotonique tels que les terpolymères acétate de vinyle / tertio-butyl benzoate de vinyle / acide crotonique et les terpolymères acide crotonique / acétate de vinyle/néododécanoate de vinyle vendus sous la dénomination Résine 28-29-30 par la société NATIONAL STARCH, les polymères dérivés d'acides ou d'anhydrides maleique, fumarique, itaconique avec des esters vinyliques, des éthers vinyliques, des halogénures vinyliques, des dérivés phénylvi- nyliques, l'acide acrylique et ses esters tels que le copolymere méthylvinylé- ther/anhydride maleique mono estérifié vendu sous la dénomination GANTREZ ES 425 par la société ISP, les copolymères d'acide méthacrylique et de méthacrylate de méthyle vendus sous la dénomination EUDRAGIT L par la société ROHM PHARMA, le copolymere d'acide méthacrylique et d'acrylate d'éthyle vendu sous la dénomination LUVIMER MAEX ou MAE par la société BASF, le copolymere acétate de vinyle/acide crotonique vendu sous la dénomination LUVISET CA 66 par la société BASF et le copolymere acétate de vinyle/acide crotonique greffé par du polyéthylèneglycol sous la dénomination ARISTOFLEX A par la société BASF.According to the invention, the anionic film-forming polymers are preferably chosen from acrylic acid copolymers such as the acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymer sold under the name ULTRAHOLD STRONG by the company BASF, the copolymers derived from crotonic acid such as the vinyl acetate / vinyl tert-butyl benzoate / crotonic acid terpolymers and the crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers sold under the name Resin 28-29-30 by the company NATIONAL STARCH, polymers derived from maleic, fumaric or itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters such as the methylvinylether / maleic anhydride copolymer mono esterified sold under the name GANTREZ ES 425 by the company ISP, metha acid copolymers and methyl methacrylate sold under the name EUDRAGIT L by the company ROHM PHARMA, the copolymer of methacrylic acid and ethyl acrylate sold under the name LUVIMER MAEX or MAE by the company BASF, the vinyl acetate / crotonic acid sold under the name LUVISET CA 66 by the company BASF and the vinyl acetate / acid copolymer crotonic grafted with polyethylene glycol under the name ARISTOFLEX A by the company BASF.
Les polymères filmogènes anioniques les plus particulièrement préférés sont choisis parmi le copolymere méthylvinyléther / anhydride maleique mono estérifié vendu sous la dénomination GANTREZ ES 425 par la société ISP, le terpolymère acide acrylique / acrylate d'éthyle / N-tertiobutylacrylamide vendu sous la dénomination ULTRAHOLD STRONG par la société BASF, les copolymères d'acide méthacrylique et de méthacrylate de méthyle vendus sous la dénomination EUDRAGIT L par la société ROHM PHARMA, les terpolymères acétate de vinyle / tertio-butyl benzoate de vinyle / acide crotonique et les terpolymères acide crotonique / acétate de vinyle / néododécaπoate de vinyle vendus sous la dénomination Résine 28-29-30 par la société NATIONAL STARCH, le copolymere d'acide méthacrylique et d'acrylate d'éthyle vendu sous la dénomination LUVIMER MAEX OU MAE par la société BASF, le terpolymère de vinyipyrroiidone / acide acrylique/méthacrylate de lauryle vendu sous la dénomination ACRYLIDONE LM par la société ISP.The most particularly preferred anionic film-forming polymers are chosen from the methyl ester / mono esterified maleic anhydride copolymer sold under the name GANTREZ ES 425 by the company ISP, the acrylic acid / ethyl acrylate / N-tertiobutylacrylamide terpolymer sold under the name ULTRAHOLD STRONG by the company BASF, the copolymers of methacrylic acid and methyl methacrylate sold under the name EUDRAGIT L by the company ROHM PHARMA, the vinyl acetate / tert-butyl vinyl benzoate / crotonic acid terpolymers and the crotonic acid / acetate terpolymers of vinyl / vinyl neododecaπoate sold under the name Resin 28-29-30 by the company NATIONAL STARCH, the copolymer of methacrylic acid and ethyl acrylate sold under the name LUVIMER MAEX OR MAE by the company BASF, the terpolymer vinyipyrroiidone / acrylic acid / lauryl methacrylate sold penny s the name ACRYLIDONE LM by the company ISP.
Les polymères filmogènes amphotères utilisables conformément à l'invention peuvent être choisis parmi les polymères comportant des motifs B et C répartis statistiquement dans la chaîne polymère où B désigne un motif dérivant d'un monomère comportant au moins un atome d'azote basique et C désigne un motif dérivant d'un monomère acide comportant un ou plusieurs groupements carboxyliques ou sulfoniques ou bien B et C peuvent désigner des groupe- ments dérivant de monomères zwittérioniques de carboxybétaïnes ou de sulfo- bétaïnes;The amphoteric film-forming polymers which can be used in accordance with the invention can be chosen from polymers comprising units B and C distributed statistically in the polymer chain where B denotes a unit derived from a monomer comprising at least one basic nitrogen atom and C denotes a unit deriving from an acidic monomer comprising one or more carboxylic or sulphonic groups or else B and C may denote groups deriving from zwitterionic monomers of carboxybetaines or of sulfobetaines;
B et C peuvent également désigner une chaîne polymère catioπique comportant des groupements aminé primaire, secondaire, tertiaire ou quaternaire, dans laquelle au moins l'un des groupements aminé porte un groupement car- boxylique ou sulfonique relié par l'intermédiaire d'un radical hydrocarboné ou bien B et C font partie d'une chaîne d'un polymère à motif éthylène α,β- dicarboxylique dont l'un des groupements carboxyliques a été amené à réagir avec une polyamine comportant un ou plusieurs groupements amine primaire ou secondaire.B and C can also denote a catalytic polymer chain comprising primary, secondary, tertiary or quaternary amine groups, in which at least one of the amine groups carries a carboxylic or sulphonic group linked via a hydrocarbon radical or else B and C are part of a chain of a polymer with an ethylene unit α, β- dicarboxylic acid, one of the carboxyl groups of which has been reacted with a polyamine comprising one or more primary or secondary amine groups.
Les polymères filmogènes amphotères répondant à la définition donnée ci- dessus plus particulièrement préférés sont choisis parmi les polymères sui- vants :The amphoteric film-forming polymers corresponding to the definition given above which are more particularly preferred are chosen from the following polymers:
1 ) les polymères résultant de la copolymérisation d'un monomère dérivé d'un composé vinylique portant un groupement carboxylique tel que plus particulièrement l'acide acrylique, l'acide méthacrylique, l'acide maléïque, l'acide alpha-chloracrylique, et d'un monomère basique dérivé d'un composé vinylique substitué contenant au moins un atome basique tel que plus particulièrement les dialkylaminoalkylméthacrylate et acrylate, les dialkylaminoalkyl- méthacrylamide et acrylamide. De tels composés sont décrits dans le brevet américain n° 3 836 537.1) polymers resulting from the copolymerization of a monomer derived from a vinyl compound carrying a carboxylic group such as more particularly acrylic acid, methacrylic acid, maleic acid, alpha-chloroacrylic acid, and d 'a basic monomer derived from a substituted vinyl compound containing at least one basic atom such as more particularly the dialkylaminoalkylmethacrylate and acrylate, the dialkylaminoalkylmethacrylamide and acrylamide. Such compounds are described in US Patent 3,836,537.
(2) les polymères comportant des motifs dérivant : a) d'au moins un monomère choisi parmi les acrylamides ou les méthacrylamides substitués sur l'azote par un radical alkyle, b) d'au moins un comonomère acide contenant un ou plusieurs groupements carboxyliques réactifs, et c) d'au moins un comonomère basique tel que des esters à substi- tuants amine primaire, secondaire, tertiaire et quaternaire des acides acrylique et méthacrylique et le produit de quatemisation du méthacrylate de diméthyl- âminoéthyle avec le sulfate de diméthyle ou diéthyle.(2) polymers comprising units derived from: a) at least one monomer chosen from acrylamides or methacrylamides substituted on nitrogen by an alkyl radical, b) from at least one acidic comonomer containing one or more carboxylic groups reagents, and c) at least one basic comonomer such as esters with primary, secondary, tertiary and quaternary amine substituents of acrylic and methacrylic acids and the product of quaternization of dimethylaminoethyl methacrylate with dimethyl sulfate or diethyl.
Les acrylamides ou méthacrylamides N-substitués plus particulièrement préférés selon l'invention sont les groupements dont les radicaux alkyle contiennent de 2 à 12 atomes de carbone et plus particulièrement le N-éthylacrylamide, le N-tertiobutyl acrylamide, le N-tertiooctyl acrylamide, le N-octylacrylamide, le N- décylacrylamide, le N-dodécylacrylamide ainsi que les méthacrylamides correspondants. Les comonomères acides sont choisis plus particulièrement parmi les acides acrylique, méthacrylique, crotonique, itaconique, maléïque, fumarique ainsi que les monoesters d'alkyle ayant 1 à 4 atomes de carbone des acides ou des anhydrides maléïque ou fumarique.The N-substituted acrylamides or methacrylamides which are more particularly preferred according to the invention are groups whose alkyl radicals contain from 2 to 12 carbon atoms and more particularly N-ethylacrylamide, N-tertiobutyl acrylamide, N-tertiooctyl acrylamide, N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide as well as the corresponding methacrylamides. The acid comonomers are chosen more particularly from acrylic, methacrylic, crotonic, itaconic, maleic, fumaric acids as well as alkyl monoesters having 1 to 4 carbon atoms of maleic or fumaric acids or anhydrides.
Les comonomères basiques préférés sont des méthacrylates d'aminoéthyle, de butyl aminoéthyle, de N,N'-diméthylaminoéthyle, de N-tertio-butylaminoéthyle. On utilise particulièrement les copolymères dont la dénomination CTFA (4ème Ed., 1991 ) est Octylacrylamide/acrylates/butylaminoethylmethacrylate copoly- mer tels que les produits vendus sous la dénomination AMPHOMER ou LOVOCRYL 47 par la société NATIONAL STARCH.The preferred basic comonomers are aminoethyl, butyl aminoethyl, N, N'-dimethylaminoethyl, N-tert-butylaminoethyl methacrylates. Copolymers are particularly used whose name CTFA (4th Ed., 1991) is Octylacrylamide / acrylates / butylaminoethylmethacrylate copolymer such as the products sold under the name AMPHOMER or LOVOCRYL 47 by the company NATIONAL STARCH.
(3) les polyamino amides réticulés et alcoylés partiellement ou totalement dérivant de polyaminoamides de formule générale :(3) crosslinked and alkylated polyamino amides partially or totally derived from polyaminoamides of general formula:
H=co — Rio— ∞ — z-3- ('") dans laquelle R-jn représente un radical divalent dérivé d'un acide dicarboxyli- que saturé, d'un acide aliphatique mono ou dicarboxylique à double liaison éthylénique, d'un ester d'un alcanol inférieur ayant 1 à 6 atome de carbone de ces acides ou d'un radical dérivant de l'addition de l'un quelconque desdits acides avec une amine bis primaire ou bis secondaire, et Z désigne un radical d'une polyalkylène-polyamine bis-primaire, mono ou bis-secondaire et de préférence représente : a) dans les proportions de 60 à 100 moles %, le radicalH = co - Rio— ∞ - z-3- ( '" ) in which R-jn represents a divalent radical derived from a saturated dicarboxylic acid, from a mono or dicarboxylic aliphatic acid with ethylene double bond, from an ester of a lower alkanol having 1 to 6 carbon atoms of these acids or of a radical derived from the addition of any one of said acids with a primary bis or secondary bis amine, and Z denotes a radical of a bis-primary, mono or bis-secondary polyalkylene polyamine and preferably represents: a) in the proportions of 60 to 100 mol%, the radical
Figure imgf000021_0001
où x=2 et p=2 ou 3, ou bien x=3 et p=2 ce radical dérivant de la diéthylène triamine, de la triéthylène tétraamine ou de la dipropylène triamine; b) dans les proportions de 0 à 40 moles % le radical (IV) ci-dessus, dans lequel x=2 et p=1 et qui dérive de l'éthylènediamine, ou le radical dérivant de la pipérazine :
Figure imgf000021_0001
where x = 2 and p = 2 or 3, or else x = 3 and p = 2 this radical deriving from diethylene triamine, triethylene tetraamine or dipropylene triamine; b) in the proportions of 0 to 40 mol% the radical (IV) above, in which x = 2 and p = 1 and which derives from ethylenediamine, or the radical deriving from piperazine:
/ \ N N/ \ N N
\ / c) dans les proportions de 0 à 20 moles % le radical -NH-(CH2)6-NH- dérivant de l'hexaméthylènediamine, ces polyaminoamines étant réticulées par addition d'un agent réticulant bifonctionnel choisi parmi les épihaiohydhnes, les diépoxydes, les dianhydrides, les dérivés bis insaturés, au moyen de 0,025 à 0,35 mole d'agent réticulant par groupement amine du polyaminoamide et al- coyïés par action d'acide acrylique, d'acide chloracétique ou d'une alcane sul- tone ou de leurs sels.\ / c) in the proportions of 0 to 20 mol% the radical -NH- (CH2) 6-NH- deriving from hexamethylenediamine, these polyaminoamines being crosslinked by addition of a bifunctional crosslinking agent chosen from epihaiohydhnes, diepoxides, dianhydrides, the bis unsaturated derivatives, using 0.025 to 0.35 mole of crosslinking agent by amine group of the polyaminoamide and alkylated by the action of acrylic acid, chloroacetic acid or a sodium alkane or their salts.
Les acides carboxyliques saturés sont choisis de préférence parmi les acides ayant 6 à 10 atomes de carbone tels que l'acide adipique, triméthyl-2,2,4- adipique et triméthyl-2,4,4-adiρique, téréphtalique, les acides à double liaison éthylénique comme par exemple les acides acrylique, méthacrylique, itaconique.The saturated carboxylic acids are preferably chosen from acids having 6 to 10 carbon atoms such as adipic, trimethyl-2,2,4-adipic acid and trimethyl-2,4,4-adiρique, terephthalic acid, ethylenic double bond such as for example acrylic, methacrylic, itaconic acids.
Les alcanes sultones utilisées dans l'alcoylation sont de préférence la propane ou la butane sultone, les sels des agents d'alcoylation sont de préférence les sels de sodium ou de potassium.The alkane sultones used in the alkylation are preferably propane or butane sultone, the salts of the alkylating agents are preferably the sodium or potassium salts.
(4) les polymères comportant des motifs zwittérioniques de formule :(4) polymers comprising zwitterionic units of formula:
Figure imgf000022_0001
dans laquelle R-| -| désigne un groupement insaturé polymérisable tel qu'un groupement acrylate, méthacrylate, acrylamide ou methacrylamide, y et z re- présente un nombre entier de 1 à 3, R^ et R13 représentent un atome d'hydrogène, méthyle, éthyle ou propyle, R14 et R15 représentent un atome d'hydrogène ou un radical alkyle de telle façon que la somme des atomes de carbone dans R-| 4 et R-15 ne dépasse pas 10. Les polymères comprenant de telles unités peuvent également comporter des motifs dérivés de monomères non zwittérioniques tels que l'acrylate ou le méthacrylate de diméthyl ou diéthyiaminoéthyle ou des alkyle acrylates ou métha- crylates, des acrylamides ou méthacrylamides ou l'acétate de vinyle. A titre d'exemple, on peut citer le copolymere de méthacrylate de méthyle / di- méthyl carboxyméthylammonio ethylméthacrylate de méthyle tel que le produit vendu sous la dénomination DIAFORMER Z301 par la société SANDOZ.
Figure imgf000022_0001
in which R- | - | denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represents an integer from 1 to 3, R ^ and R13 represent a hydrogen, methyl, ethyl or propyl atom, R14 and R15 represent a hydrogen atom or an alkyl radical such that the sum of the carbon atoms in R- | 4 and R-15 does not exceed 10. The polymers comprising such units may also contain units derived from non-zwitterionic monomers such as dimethyl or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates, acrylamides or methacrylamides or vinyl acetate. By way of example, there may be mentioned the copolymer of methyl methacrylate / di-methyl carboxymethylammonio ethyl methacrylate such as the product sold under the name DIAFORMER Z301 by the company SANDOZ.
(5) les polymères dérivés du chitosane comportant des motifs monomères répondant aux formules suivantes :(5) polymers derived from chitosan containing monomer units corresponding to the following formulas:
Figure imgf000023_0001
le motif D étant présent dans des proportions comprises entre 0 et 30%, le motif E dans des proportions comprises entre 5 et 50% et le motif F dans des proportions comprises entre 30 et 90%, étant entendu que dans ce motif F, R16 représente un radical de formule :
Figure imgf000023_0001
the motif D being present in proportions of between 0 and 30%, the motif E in proportions of between 5 and 50% and the motif F in proportions of between 30 and 90%, it being understood that in this motif F, R 16 represents a radical of formula:
Figure imgf000023_0002
dans laquelle si q=0, R- γ, R18 et R-|g, identiques ou différents, représentent chacun un atome d'hydrogène, un reste méthyle, hydroxyle, acétoxy ou amino, un reste monoalcoylamine ou un reste dialcoylamine éventuellement interrompus par un ou plusieurs atomes d'azote et/ou éventuellement substitués par un ou plusieurs groupes amine, hydroxyle, carboxyle, alcolylthio, sulfonique, un reste alcoylthio dont le groupe alcoyle porte un reste amino, l'un au moins des radicaux R17, R«ιs et R-jg étant dans ce cas un atome d'hydrogène ; ou si q=1 , R<|7, R-|8 et R<|g représentent chacun un atome d'hydrogène, ainsi que les sels formés par ces composés avec des bases ou des acides.
Figure imgf000023_0002
in which if q = 0, R- γ, R18 and R- | g, identical or different, each represent a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkylamine residue or a dialkylamine residue possibly interrupted by one or more nitrogen atoms and / or optionally substituted by one or more amine, hydroxyl, carboxyl, alcolylthio, sulfonic groups, an alkylthio residue in which the alkyl group carries an amino residue, at least one of the radicals R17, R " ιs and R-jg being in this case a hydrogen atom; or if q = 1, R <| 7, R- | 8 and R < | g each represent a hydrogen atom, as well as the salts formed by these compounds with bases or acids.
(6) Les polymères dérivés de la N-carboxyalkylation du chitosane comme le N-carboxyméthyl chitosane ou le N-carboxybutyl chitosane vendu sous la dénomination "EVALSAN" par la société JAN DEKKER. (7) Les polymères répondant à la formule générale (VI) par exemple décrits dans le brevet français 1 400 366 :(6) Polymers derived from the N-carboxyalkylation of chitosan such as N-carboxymethyl chitosan or N-carboxybutyl chitosan sold under the name "EVALSAN" by the company JAN DEKKER. (7) The polymers corresponding to the general formula (VI), for example described in French patent 1,400,366:
Figure imgf000024_0001
dans laquelle R20 représente un atome d'hydrogène, un radical CH3O, CH3CH2O, phényle, R2 désigne l'hydrogène ou un radical alkyle inférieur tel que méthyle, éthyle, R22 désigne l'hydrogène ou un radical alkyle inférieur tel que méthyle, éthyle, R23 désigne un radical alkyle inférieur tel que méthyle, éthyle ou un radical répondant à la formule : -R24-N(R22)2> R24 représentant un groupement -CH2-CH2- , -CH2-CH2-CH2- , -CH2-CH(CH3)- , R22 ayant les significations mentionnées ci-dessus, ainsi que les homologues supérieurs de ces radicaux et contenant jusqu'à 6 atomes de carbone.
Figure imgf000024_0001
in which R20 represents a hydrogen atom, a CH3O radical, CH3CH2O, phenyl, R2 denotes hydrogen or a lower alkyl radical such as methyl, ethyl, R22 denotes hydrogen or a lower alkyl radical such as methyl, ethyl, R23 denotes a lower alkyl radical such as methyl, ethyl or a radical corresponding to the formula: -R24-N (R22) 2 > R 24 representing a group -CH2-CH2-, -CH 2 -CH 2 -CH 2 -, -CH 2 -CH (CH 3 ) -, R 2 2 having the meanings mentioned above, as well as the higher homologs of these radicals and containing up to 6 carbon atoms.
(8) Des polymères amphotères du type -D-X-D-X- choisis parmi: a) les polymères obtenus par action de l'acide chloracétique ou le chlora- cétate de sodium sur les composés comportant au moins un motif de formule :(8) Amphoteric polymers of the type -D-X-D-X- chosen from: a) the polymers obtained by the action of chloracetic acid or sodium chloracetate on the compounds comprising at least one unit of formula:
-D-X-D-X-D- (VII)-D-X-D-X-D- (VII)
OÙ D désigne un radicalWHERE D denotes a radical
/ \/ \
-N N-N N
\ / et X désigne le symbole E ou E', E ou E' identiques ou différents désignent un radical bivalent qui est un radical alkylène à chaîne droite ou ramifiée comportant jusqu'à 7 atomes de carbone dans la chaîne principale non substituée ou substituée par des groupements hydroxyle et pouvant comporter en outre des atomes d'oxygène, d'azote, de soufre, 1 à 3 cycles aromatiques et/ou hétéro- cycliques; les atomes d'oxygène, d'azote et de soufre étant présents sous forme de groupements éther, thioéther, sulfoxyde, sulfone, sulfonium, alkyla- mine, alkénylamine, des groupements hydroxyle, benzylamine, oxyde d'aminé, ammonium quaternaire, amide, imide, alcool, ester et/ou uréthanne. b) Les polymères de formule :\ / and X denotes the symbol E or E ', E or E', which are identical or different, denote a bivalent radical which is an alkylene radical with a straight or branched chain containing up to 7 carbon atoms in the unsubstituted main chain or substituted by hydroxyl groups and which may additionally contain oxygen, nitrogen, sulfur atoms, 1 to 3 aromatic and / or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine, alkenylamine groups, hydroxyl groups, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and / or urethane. b) The polymers of formula:
-D-X-D-X- (VI I') où D désigne un radical-D-X-D-X- (VI I ') where D denotes a radical
/ \/ \
-N ] N--N] N-
\ / et X désigne le symbole E ou E' et au moins une fois E'; E ayant la signification indiquée ci-dessus et E' est un radical bivalent qui est un radical alkylène à chaîne droite ou ramifiée ayant jusqu'à 7 atomes de carbone dans la chaîne principale, substitué ou non par un ou plusieurs radicaux hydroxyle et compor- tant un ou plusieurs atomes d'azote, l'atome d'azote étant substitué par une chaîne alkyle interrompue éventuellement par un atome d'oxygène et comportant obligatoirement une ou plusieurs fonctions carboxyle ou une ou plusieurs fonctions hydroxyle et bétaïnisées par réaction avec l'acide chloracétique ou du chloracétate de soude.\ / and X denotes the symbol E or E 'and at least once E'; E having the meaning indicated above and E 'is a bivalent radical which is a straight or branched chain alkylene radical having up to 7 carbon atoms in the main chain, substituted or not by one or more hydroxyl radicals and comprising as one or more nitrogen atoms, the nitrogen atom being substituted by an alkyl chain optionally interrupted by an oxygen atom and necessarily having one or more carboxyl functions or one or more hydroxyl functions and betainized by reaction with chloracetic acid or sodium chloracetate.
(9) les copolymères alkyl(C1-C5)vinyléther / anhydride maleique modifié partiellement par semiamidification avec une N,N-dialkylaminoalkylamine telle que la N,N-diméthylaminopropylamine ou par semiestérification avec une N,N- dialcanolamine. Ces copolymères peuvent également comporter d'autres co- monomères vinyliques tels que le vinylcaprolactame.(9) alkyl (C1-C5) vinyl ether / maleic anhydride copolymers partially modified by semiamidification with an N, N-dialkylaminoalkylamine such as N, N-dimethylaminopropylamine or by semiesterification with an N, N-dialcanolamine. These copolymers can also contain other vinyl co-monomers such as vinylcaprolactam.
Les polymères filmogènes amphotères particulièrement préférés selon l'invention sont ceux de la famille (3) tels que les copolymères dont la dénomination CTFA est Octylacrylamide/acrylates/butylaminoethylmethacrylate copolymer tels que les produits vendus sous les dénominations AMPHOMER, AMHOMER LV 71 ou LOVOCRYL 47 par la société NATIONAL STARCH et ceux de la fa- mille (4) tels que les copolymere de méthacrylate de méthyle / diméthyl carboxyméthylammonio ethylméthacrylate de méthyle par exemple vendu sous la dénomination DIAFORMER Z301 par la société SANDOZ.The amphoteric film-forming polymers which are particularly preferred according to the invention are those of the family (3) such as the copolymers whose name CTFA is Octylacrylamide / acrylates / butylaminoethylmethacrylate copolymer such as the products sold under the names AMPHOMER, AMHOMER LV 71 or LOVOCRYL 47 by NATIONAL STARCH and those of the fa- thousand (4) such as the copolymers of methyl methacrylate / dimethyl carboxymethylammonio ethyl methyl methacrylate, for example sold under the name DIAFORMER Z301 by the company SANDOZ.
Les polymères filmogènes non ioniques utilisables selon la présente invention sont choisis par exemple parmi :The nonionic film-forming polymers which can be used according to the present invention are chosen, for example, from:
- les homopolymères de vinyipyrroiidone ;- homopolymers of vinyipyrroiidone;
- les copolymères de vinyipyrroiidone et d'acétate de vinyle ;- copolymers of vinyipyrroiidone and vinyl acetate;
- les polyalkyloxazolines telles que les polyéthyloxazoiines proposées par la société DOW CHEMICAL sous les dénominations PEOX 50 000, PEOX- polyalkyloxazolines such as polyethyloxazoiines offered by the company DOW CHEMICAL under the names PEOX 50 000, PEOX
200 000 et PEOX 500 000 ;200,000 and PEOX 500,000;
- les homopolymères d'acétate de vinyle tels que le produit proposé sous le nom de APPRETAN EM par la société HOECHST ou le produit proposé sous le nom de RHODOPAS A 012 par la société RHONE POULENC ; - les copolymères d'acétate de vinyle et d'ester acrylique tels que le produit proposé sous le nom de RHODOPAS AD 310 de RHONE POULENC ;- vinyl acetate homopolymers such as the product offered under the name of APPRETAN EM by the company HOECHST or the product offered under the name of RHODOPAS A 012 by the company RHONE POULENC; - the vinyl acetate and acrylic ester copolymers such as the product offered under the name RHODOPAS AD 310 from RHONE POULENC;
- les copolymères d'acétate de vinyle et d'éthylène tels que le produit proposé sous le nom de APPRETAN TV par la société HOECHST ;- copolymers of vinyl acetate and ethylene such as the product offered under the name of APPRETAN TV by the company HOECHST;
- les copolymères d'acétate de vinyle et d'ester maléïque par exemple de ma- léate de dibutyle tels que le produit proposé sous le nom de APPRETAN MB- the copolymers of vinyl acetate and of maleic ester, for example of dibutyl maleate such as the product offered under the name of APPRETAN MB
EXTRA par la société HOECHST ;EXTRA by HOECHST;
- les copolymères de polyéthylène et d'anhydride maléïque ;- copolymers of polyethylene and maleic anhydride;
- les homopolymères d'acrylates d'alkyle et les homopolymères de méthacry- lates d'alkyle tels que le produit proposé sous la dénomination MICROPEARL RQ 750 par la société MATSUMOTO ou le produit proposé sous la dénomination LUHYDRAN A 848 S par la société BASF ;homopolymers of alkyl acrylates and homopolymers of alkyl methacrylates such as the product offered under the name MICROPEARL RQ 750 by the company MATSUMOTO or the product offered under the name LUHYDRAN A 848 S by the company BASF;
- les copolymères d'esters acryliques tels que par exemple les copolymères d'acrylates d'alkyle et de méthacrylates d'alkyles tels que les produits proposés par la société ROHM&HAAS sous les dénominations PRIMAL AC-261 K et EUDRAGIT NE 30 D, par la société BASF sous les dénominations ACRONAL 601 , LUHYDRAN LR 8833 ou 8845, par la société HOECHST sous les dénominations APPRETAN N 9213 ou N9212; - les copolymères d'acrylonitrile et d'un monomère non ionique choisi par exemple parmi le butadiène et les (méth)acrylates d'alkyle ; on peut citer les produits proposés sous les dénominations NIPOL LX 531 B par la société NIPPON ZEON ou ceux proposés sous la dénomination CJ 0601 B par la so- ciété ROHM & HAAS ;- copolymers of acrylic esters such as for example copolymers of alkyl acrylates and of alkyl methacrylates such as the products offered by the company ROHM & HAAS under the names PRIMAL AC-261 K and EUDRAGIT NE 30 D, by the BASF under the names ACRONAL 601, LUHYDRAN LR 8833 or 8845, by the company HOECHST under the names APPRETAN N 9213 or N9212; - copolymers of acrylonitrile and of a nonionic monomer chosen, for example, from butadiene and alkyl (meth) acrylates; mention may be made of the products offered under the name NIPOL LX 531 B by the company NIPPON ZEON or those offered under the name CJ 0601 B by the company ROHM &HAAS;
- les polyuréthannes tels que les produits proposés sous les dénominations ACRYSOL RM 1020 ou ACRYSOL RM 2020 par la société ROHM & HAAS, les produits URAFLEX XP 401 UZ, URAFLEX XP 402 UZ par la société DSM RESINS ; - les copolymères d'acrylate d'alkyle et d'uréthanne tels que le produit 8538-33 par la société NATIONAL STARCH ;- polyurethanes such as the products offered under the names ACRYSOL RM 1020 or ACRYSOL RM 2020 by the company ROHM & HAAS, the products URAFLEX XP 401 UZ, URAFLEX XP 402 UZ by the company DSM RESINS; - copolymers of alkyl acrylate and urethane such as the product 8538-33 by the company NATIONAL STARCH;
- les polyamides tels que le produit ESTAPOR LO 11 proposé par la société RHONE POULENC.- polyamides such as the product ESTAPOR LO 11 offered by the company RHONE POULENC.
- les gommes de guar non ioniques chimiquement modifiées ou non modifiées. Les gommes de guar non ioniques non modifiées sont par exemple les produits vendus sous la dénomination VIDOGUM GH 175 par la société UNIPECTINE et sous la dénomination JAGUAR C par la société MEYHALL. Les gommes de guar non-ioniques modifiées utilisables selon l'invention sont de préférence modifiées par des groupements hydroxyalkylé en Ci-C 6- On peut mentionner à titre d'exemple, les groupements hydroxyméthyle, hydroxyéthyle, hydroxypropyle et hydroxybutyle.- chemically modified or unmodified nonionic guar gums. Unmodified non-ionic guar gums are for example the products sold under the name VIDOGUM GH 175 by the company UNIPECTINE and under the name JAGUAR C by the company MEYHALL. The modified nonionic guar gums which can be used according to the invention are preferably modified with C 1 -C 6 hydroxyalkyl groups. Mention may be made, by way of example, of the hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.
Ces gommes de guar sont bien connues de l'état de la technique et peuvent par exemple être préparées en faisant réagir des oxydes d'alcènes correspondants, tels que par exemple des oxydes de propylene, avec la gomme de guar de façon à obtenir une gomme de guar modifiée par des groupements hydroxypropyle.These guar gums are well known in the state of the art and can for example be prepared by reacting corresponding alkene oxides, such as for example propylene oxides, with guar gum so as to obtain a gum of guar modified by hydroxypropyl groups.
De telles gommes de guar non-ioniques éventuellement modifiées par des groupements hydroxyalkylé sont par exemple vendues sous les dénominations commerciales JAGUAR HP8, JAGUAR HP60 et JAGUAR HP120, JAGUAR DC 293 et JAGUAR HP 105 par la société MEYHALL, ou sous la dénomination GALACTASOL 4H4FD2 par la société AQUALON. Les radicaux alkyle des polymères non ioniques ont de 1 à 6 atomes de carbone sauf mention contraire.Such nonionic guar gums possibly modified with hydroxyalkyl groups are for example sold under the trade names JAGUAR HP8, JAGUAR HP60 and JAGUAR HP120, JAGUAR DC 293 and JAGUAR HP 105 by the company MEYHALL, or under the name GALACTASOL 4H4FD2 the AQUALON company. The alkyl radicals of nonionic polymers have from 1 to 6 carbon atoms unless otherwise stated.
Selon l'invention, on peut également utiliser les polymères filmogènes de type siliconés greffés comprenant une portion polysiloxane et une portion constituée d'une chaîne organique non-siliconée, l'une des deux portions constituant la chaîne principale du polymère l'autre étant greffée sur la dite chaîne principale. Ces polymères sont par exemple décrits dans les demandes de brevet EP-A- 0412 704, EP-A-0 412 707, EP-A-0 640 105 et WO 95/00578, EP-A-0582 152 et WO 93/23009 et les brevets US 4,693,935, US 4,728,571 et US 4,972,037. Ces polymères sont de préférence anioniques ou non ioniques. De tels polymères sont par exemple les copolymères susceptibles d'être obtenus par polymérisation radicalaire à partir du mélange de monomères constitué par : a) 50 à 90% en poids d'acrylate de tertiobutyle ; b) 0 à 40% en poids d'acide acrylique ; c) 5 à 40% en poids de macromère silicone de formule :According to the invention, it is also possible to use film-forming polymers of the grafted silicone type comprising a polysiloxane portion and a portion consisting of a non-silicone organic chain, one of the two portions constituting the main chain of the polymer the other being grafted on the said main channel. These polymers are for example described in patent applications EP-A-0412 704, EP-A-0 412 707, EP-A-0 640 105 and WO 95/00578, EP-A-0582 152 and WO 93/23009 and US patents 4,693,935, US 4,728,571 and US 4,972,037. These polymers are preferably anionic or nonionic. Such polymers are, for example, the copolymers capable of being obtained by radical polymerization from the mixture of monomers consisting of: a) 50 to 90% by weight of tert-butyl acrylate; b) 0 to 40% by weight of acrylic acid; c) 5 to 40% by weight of silicone macromer of formula:
CH '2, = ( CH2 ) 3- - CH,CH '2, = (CH 2 ) 3 - - CH,
Figure imgf000028_0001
avec v étant un nombre allant de 5 à 700 ; les pourcentages en poids étant calculés par rapport au poids total des monomères.
Figure imgf000028_0001
with v being a number ranging from 5 to 700; the weight percentages being calculated relative to the total weight of the monomers.
D'autres exemples de polymères siliconés greffés sont notamment des polydi- méthylsiloxanes (PDMS) sur lesquels sont greffés, par l'intermédiaire d'un chaînon de raccordement de type thiopropylène, des motifs polymères mixtes du type acide poly(méth)acrylique et du type poly(méth)acrylate d'alkyle et des polydiméthylsiloxanes (PDMS) sur lesquels sont greffés, par l'intermédiaire d'un chaînon de raccordement de type thiopropylène, des motifs polymères du type poly(méth)acrylate d'isobutyle. On peut aussi utiliser, comme polymères filmogènes (B), des polyuréthannes fonctionnalisés ou non, siliconés ou non, différents des polycondensats (A).Other examples of grafted silicone polymers are in particular polydimethylsiloxanes (PDMS) onto which are grafted, via a thiopropylene-type connecting link, mixed polymer units of the poly (meth) acrylic acid type and poly (meth) acrylate type and polydimethylsiloxanes (PDMS) onto which are grafted, via a thiopropylene type connecting link, polymer units of the poly (meth) acrylate type isobutyl. It is also possible to use, as film-forming polymers (B), polyurethanes functionalized or not, silicone or not, different from the polycondensates (A).
Le moyen de distribution, qui forme une partie du dispositif flacon pompe, est généralement constitué par au moins une pompe fonctionnant pour l'aspiration et/ou le refoulement du liquide et de l'air. Cette pompe est commandée par une tête de distribution, elle même comprenant une buse par laquelle la composition est vaporisée.The distribution means, which forms part of the pump bottle device, generally consists of at least one pump operating for the suction and / or delivery of the liquid and the air. This pump is controlled by a dispensing head, itself comprising a nozzle by which the composition is vaporized.
Selon l'invention, on utilise avantageusement un dispositif flacon pompe qui délivre une quantité de composition comprise entre 120 et 170 μl lorsque l'utilisateur applique 1 pression sur le bouton poussoir, et de préférence une quantité de composition comprise entre 140 et 160 μl.According to the invention, a pump bottle device is advantageously used which delivers an amount of composition between 120 and 170 μl when the user applies 1 press on the push button, and preferably an amount of composition between 140 and 160 μl.
Conformément à l'invention, le diamètre des gouttelettes est mesuré pour une température de la composition voisine de 20°C à l'intérieur du dispositif flacon pompe. En pratique, on place le dispositif flacon pompe à la température ambiante et on mesure le diamètre des gouttelettes à 20 cm de la buse.According to the invention, the diameter of the droplets is measured for a temperature of the composition close to 20 ° C. inside the pump bottle device. In practice, the pump bottle device is placed at room temperature and the diameter of the droplets is measured at 20 cm from the nozzle.
Les polycondensats utilisés conformément à l'invention peuvent être so- lubles dans le milieu cosmétiquement acceptable ou encore former une dispersion dans ce milieu. La dispersion peut comprendre alors au moins 0,05 % de tensioactif permettant la mise en dispersion et le maintien en dispersion du polycondensat.The polycondensates used in accordance with the invention may be soluble in the cosmetically acceptable medium or else form a dispersion in this medium. The dispersion can then comprise at least 0.05% of surfactant enabling the polycondensate to be dispersed and maintained in dispersion.
Selon l'invention, on peut utiliser tout type de tensioactif dans ladite dispersion, mais de préférence un tensioactif non ionique. La taille moyenne des particules du polycondensat dans la dispersion est de préférence comprise entre 0,1 et 1 micron.According to the invention, any type of surfactant can be used in said dispersion, but preferably a nonionic surfactant. The average particle size of the polycondensate in the dispersion is preferably between 0.1 and 1 micron.
La composition conforme à l'invention comprend avantageusement, en proportion relative en poids par rapport au poids total de la composition, entre 0,1 et 30 % du polycondensat (A) comprenant au moins une séquence polyuréthanne et/ou polyurée, plus avantageusement entre 0,5 et 20 %, et encore plus avantageusement entre 1 et 10 % de ce polycondensat.The composition according to the invention advantageously comprises, in relative proportion by weight relative to the total weight of the composition, between 0.1 and 30% of the polycondensate (A) comprising at least one polyurethane and / or polyurea block, more advantageously between 0.5 and 20%, and even more advantageously between 1 and 10% of this polycondensate.
La composition conforme à l'invention comprend avantageusement, en proportion relative en poids par rapport au poids total de la composition, entre 0,1 et 30 % du polymère filmogène (B), plus avantageusement entre 0,5 et 20 %, et encore plus avantageusement entre 1 et 10 % de polymère filmogène (B).The composition according to the invention advantageously comprises, in relative proportion by weight relative to the total weight of the composition, between 0.1 and 30% of the film-forming polymer (B), more advantageously between 0.5 and 20%, and again more advantageously between 1 and 10% of film-forming polymer (B).
Elle peut comprendre un solvant organique additionnel, dans une proportion variant entre 0,5 et 80 %.It can comprise an additional organic solvent, in a proportion varying between 0.5 and 80%.
Conformément à l'invention, le solvant organique est notamment choisi dans le groupe comprenant les alcools en Ci à C tels que l'éthanol ou l'iso- propanol, l'acétone, la méthyléthylcétone, l'acétate de méthyle, l'acétate de butyle, l'acétate d'éthyle, le diméthoxyéthane, le diéthoxyéthane et leurs mélanges. De manière préférentielle, on utilise l'éthanol.In accordance with the invention, the organic solvent is chosen in particular from the group comprising C1 to C alcohols such as ethanol or isopropanol, acetone, methyl ethyl ketone, methyl acetate, acetate butyl, ethyl acetate, dimethoxyethane, diethoxyethane and mixtures thereof. Preferably, ethanol is used.
Les compositions conformes à l'invention peuvent par ailleurs contenir des additifs cosmétiques conventionnels choisis notamment parmi les corps gras, les agents épaississants, les adoucissants, les agents anti-mousse, les agents hydratants, les agents antiperspirants, les agents alcalinisants, les colorants, les pigments, les parfums, les conservateurs, les tensioactifs, les poly- mères autres que ceux de l'invention, les siliconés volatiles ou non, notamment les siliconés anioniques, les polyols, les protéines et les vitamines.The compositions in accordance with the invention may also contain conventional cosmetic additives chosen in particular from fatty substances, thickening agents, softeners, anti-foaming agents, moisturizing agents, antiperspirant agents, alkalizing agents, dyes, pigments, perfumes, preservatives, surfactants, polymers other than those of the invention, volatile and non-volatile silicones, in particular anionic silicones, polyols, proteins and vitamins.
L'invention pourra être mieux comprise à l'aide de l'exemple non limitatif ci-après.The invention can be better understood using the following non-limiting example.
Exemple: On compare la qualité de la pulvérisation obtenue au moyen de flacons pompes conformes à l'invention et celle obtenue avec des flacons pompes de l'art antérieur.Example: The quality of the spraying obtained by means of pump bottles according to the invention is compared with that obtained with pump bottles of the prior art.
Les trois flacons pompes conformes à l'invention contiennent tous la même composition I comprenant un polyuréthanne et diffèrent entre eux par les moyens de distribution.The three pump bottles according to the invention all contain the same composition I comprising a polyurethane and differ from each other by the distribution means.
CompositionComposition
- Polycondensat polyester acide lactique / éthylène glycol P (MIS - EG) - acide diméthylol propanoïque (DMPA) - isophoronediisocyanate 6,6- Polycondensate polyester lactic acid / ethylene glycol P (MIS - EG) - dimethylol propanoic acid (DMPA) - isophoronediisocyanate 6.6
%%
- Polydiméthyl / méthylsiloxane à groupements propylthio-3-méthylacrylate / methylacrylate / acide méthacrylique vendu par 3M sous la dénomination- Polydimethyl / methylsiloxane containing propylthio-3-methylacrylate / methylacrylate / methacrylic acid groups sold by 3M under the name
VS80 0,1g m.aVS80 0.1g m.a
- Aminométhyl propanol qs neutralisation - Ethanol 40- Aminomethyl propanol qs neutralization - Ethanol 40
%%
- Eau déminéralisée qsp 100- Demineralized water qs 100
%%
m.a. signifie matière activemy. means active ingredient
Les flacons pompes conformes à l'art antérieur contiennent des compositions fixantes sans polyuréthanne, à savoir Mighty Mist ® commercialisé par l'Oréai et Pantène ® commercialisé par Procter & Gamble.The pump bottles in accordance with the prior art contain fixing compositions without polyurethane, namely Mighty Mist ® marketed by Oreai and Pantène ® marketed by Procter & Gamble.
Pour le conditionnement des compositions, on utilise les dispositifs: - Euromist 140 commercialisé par Seaquist et qui délivre 140 μl de composition pour 1 pression exercée par l'utilisateurFor packaging the compositions, the following devices are used: - Euromist 140 marketed by Seaquist and which delivers 140 μl of composition for 1 pressure exerted by the user
- Euromist 160 commercialisé par Seaquist et qui délivre 160 μl de composition pour 1 pression exercée par l'utilisateur, - Perfect PZ11/140 commercialisé par Valois qui délivre 140 μl de composition pour 1 pression exercée par l'utilisateur.- Euromist 160 marketed by Seaquist and which delivers 160 μl of composition for 1 pressure exerted by the user, - Perfect PZ11 / 140 marketed by Valois which delivers 140 μl of composition for 1 pressure exerted by the user.
On évalue le diamètre moyen des gouttelettes sortant des flacons pompes ainsi que les diamètres minimal et maximal. Les résultats sont résumés dans le tableau 1 ci-après.The mean diameter of the droplets leaving the pump bottles is evaluated, as well as the minimum and maximum diameters. The results are summarized in Table 1 below.
Tableau 1Table 1
Figure imgf000032_0001
Figure imgf000032_0001
II en résulte que des flacons pompes conformes à la présente invention fournissent des gouttelettes plus fines que les flacons pompes selon l'art antérieur. Les flacons pompes conformes à l'invention procurent donc une pulvérisation plus homogène du produit sur les cheveux que les flacons pompes de l'art antérieur. As a result, pump bottles according to the present invention provide finer droplets than the pump bottles according to the prior art. The pump bottles in accordance with the invention therefore provide a more homogeneous spraying of the product on the hair than the pump bottles of the prior art.

Claims

Revendications Claims
1. Dispositif flacon pompe comprenant un réservoir contenant une composition capillaire ainsi que des moyens de distribution de la composition, caractérisé par le fait que: (i) la composition comprend, dans un milieu cosmétiquement acceptable, au moins un polycondensat (A) comprenant au moins une séquence polyuréthanne et ou polyurée et au moins un polymère filmogène (B); et (ii) les polymères (A) et (B) et le dispositif étant choisis de sorte à obtenir, à la sortie du dispositif, des gouttelettes de composition de diamètre moyen infé- rieur ou égal à 80 μm.1. Pump bottle device comprising a reservoir containing a hair composition as well as means for distributing the composition, characterized in that: (i) the composition comprises, in a cosmetically acceptable medium, at least one polycondensate (A) comprising at least at least one polyurethane and or polyurea block and at least one film-forming polymer (B); and (ii) the polymers (A) and (B) and the device being chosen so as to obtain, at the outlet of the device, droplets of composition with an average diameter less than or equal to 80 μm.
2. Dispositif selon la revendication 1 , caractérisé par le fait que le diamètre moyen des gouttelettes est inférieur ou égal à 75 μm.2. Device according to claim 1, characterized in that the average diameter of the droplets is less than or equal to 75 microns.
3. Dispositif selon l'une quelconque des revendications précédentes, caractérisé par le fait que la composition contient un solvant organique.3. Device according to any one of the preceding claims, characterized in that the composition contains an organic solvent.
4. Dispositif selon l'une quelconque des revendications précédentes, caractérisé par le fait que le polycondensat est formé par un arrangement de blocs, cet arrangement étant obtenu notamment à partir de:4. Device according to any one of the preceding claims, characterized in that the polycondensate is formed by an arrangement of blocks, this arrangement being obtained in particular from:
(1 ) au moins un composé qui contient deux ou plus de deux atomes d'hy- dro gène actifs par molécule;(1) at least one compound that contains two or more than two active hydrogen atoms per molecule;
(2) au moins un diol ou un mélange de diols contenant des radicaux acides ou leurs sels; (3) au moins un di- ou polyisocyanate.(2) at least one diol or a mixture of diols containing acid radicals or their salts; (3) at least one di- or polyisocyanate.
5. Dispositif selon la revendication 4, caractérisé par le fait que les composés (1 ) sont choisis dans le groupe comprenant les diols, les diamines, les polyes- terols, les polyétherols ou leur mélange.5. Device according to claim 4, characterized in that the compounds (1) are chosen from the group comprising diols, diamines, polyesterols, polyetherols or their mixture.
6. Dispositif selon la revendication 4, caractérisé par le fait que le composé (2) est un acide carboxylique 2,2-hydroxyméthyl. 6. Device according to claim 4, characterized in that the compound (2) is a 2,2-hydroxymethyl carboxylic acid.
7. Dispositif selon la revendication 4, caractérisé par le fait que le composé (3) est choisi dans la groupe comprenant l'hexaméthylène diisocyanate, l'isopho- rondiisocyanate, le toluylendiisocyanate, le diphénylméthane 4,4'-diisocyanate, le dicyclohexylméthane 4,4'-diisocyanate, le méthylène-di-p-phényl diisocyanate, le méthylène-bis(4-cyclohexylisocyanate), l'isophorone diisocyanate, le toluène diisocyanate, le 1 ,5-naphtalène diisocyanate, le 4,4'-diphénylméthane diisocyanate, le 2,2'-diméthyl-4,4'-diphénylméthane diisocyanate, le 1 ,3- phénylène diisocyanate, le 1 ,4-phénylène diisocyanate, des mélanges de 2,4- et de 2,6- toluène diisocyanate, le 2,2'-dichloro-4,4'-diisocyanato diphénylméthane, le 2,4-dibromo-1 ,5-diisocyanato naphtalène, le 1 ,4-diisocyanate butane, l'hexane-1 ,6-diisocyanate et le cyclohexane-1 ,4-diisocyanate.7. Device according to claim 4, characterized in that the compound (3) is chosen from the group comprising hexamethylene diisocyanate, isopho-rondiisocyanate, toluylendiisocyanate, diphenylmethane 4,4'-diisocyanate, dicyclohexylmethane 4 , 4'-diisocyanate, methylene-di-p-phenyl diisocyanate, methylene-bis (4-cyclohexylisocyanate), isophorone diisocyanate, toluene diisocyanate, 1, 5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-dimethyl-4,4'-diphenylmethane diisocyanate, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, 2,2'-dichloro-4,4'-diisocyanato diphenylmethane, 2,4-dibromo-1, 5-diisocyanato naphthalene, 1, 4-diisocyanate butane, hexane-1, 6-diisocyanate and cyclohexane -1, 4-diisocyanate.
8. Dispositif selon la revendication 4, caractérisé par le fait que le polyconden- sat est formé à partir d'au moins un composé supplémentaire ayant un squelette silicone et choisi dans le groupe comprenant les polysiloxanes, les polyal- kylsiloxanes ou les polyarylsiloxanes notamment les polyéthylsiloxanes, les polyméthylsiloxanes et les polyphénylsiloxanes, comportant éventuellement des chaînes hydrocarbonées greffées sur les atomes de silicium.8. Device according to claim 4, characterized in that the polycondensate is formed from at least one additional compound having a silicone skeleton and chosen from the group comprising polysiloxanes, polyalkylsiloxanes or polyarylsiloxanes, in particular the polyethylsiloxanes, polymethylsiloxanes and polyphenylsiloxanes, optionally comprising hydrocarbon chains grafted on the silicon atoms.
9. Dispositif selon l'une quelconque des revendications 1 à 3, caractérisé par le fait que les séquences de polyuréthanne et/ou polyurée du polymère présentent un motif répétitif de base répondant à la formule générale I' ci-après:9. Device according to any one of claims 1 to 3, characterized in that the polyurethane and / or polyurea blocks of the polymer have a basic repeating unit corresponding to the general formula I 'below:
- X' - B - X - CO - NH - R - NH - CO - (F)- X '- B - X - CO - NH - R - NH - CO - (F)
dans laquelle :in which :
- X' représente O et ou NH,- X 'represents O and or NH,
- B est un radical hydrocarboné, ce radical étant substitué ou non, et - R est un radical divalent choisi parmi les radicaux alkylène de type aromatique, aliphatique en d à C20, cycloaliphatique en Ci à C20, ces radicaux étant substitués ou non. - B is a hydrocarbon radical, this radical being substituted or not, and - R is a divalent radical chosen from alkylene radicals of aromatic type, aliphatic in D to C 20 , cycloaliphatic in Ci to C 20 , these radicals being substituted or unsubstituted .
10. Dispositif selon la revendication 9, caractérisé par le fait que B est un radical hydrocarboné bivalent en Ci à C30.10. Device according to claim 9, characterized in that B is a bivalent Ci to C 30 hydrocarbon radical.
11. Dispositif selon la revendication 9 ou 10, caractérisé par le fait que le radical R est choisi dans le groupe comprenant les radicaux hexaméthylène, 4,4'- biphénylèneméthane, 2,4- et/ou 2,6-tolylène, 1 ,5-naphtylène, p-phénylène, méthylène- 4,4bis - cyclohexyle et le radical divalent dérivé de l'isophorone.11. Device according to claim 9 or 10, characterized in that the radical R is chosen from the group comprising the hexamethylene, 4,4'-biphenylenemethane, 2,4- and / or 2,6-tolylene radicals, 1, 5-naphthylene, p-phenylene, methylene-4,4bis - cyclohexyl and the divalent radical derived from isophorone.
12. Dispositif selon l'une quelconque des revendications 1 à 3, caractérisé par le fait que le polycondensat présente un motif répétitif de base répondant à la formule (M'):12. Device according to any one of claims 1 to 3, characterized in that the polycondensate has a basic repeating unit corresponding to the formula (M '):
- X' - P - X' - CO - NH - R - NH - CO - (II")- X '- P - X' - CO - NH - R - NH - CO - (II ")
dans laquelle :in which :
- P est un segment polysiloxanique,- P is a polysiloxane segment,
- X' représente O et ou NH, et - R est un radical divalent choisi parmi les radicaux alkylène de type aromatique, aliphatique en Ci à C20, cycloaliphatique en Ci à C20, ces radicaux étant substitués ou non.- X 'represents O or NH and, and - R is a divalent radical chosen from alkylene radicals of aromatic type, aliphatic Ci to C 20 cycloaliphatic Ci -C 20, these radicals being substituted or unsubstituted.
13. Dispositif selon l'une quelconque des revendications précédentes, caracté- risé par le fait que la composition comprend, en proportion relative en poids, entre 0,1 et 30 % du polycondensat (A), de préférence entre 0,5 et 20 %, et plus avantageusement encore entre 1 et 10 %.13. Device according to any one of the preceding claims, characterized in that the composition comprises, in relative proportion by weight, between 0.1 and 30% of the polycondensate (A), preferably between 0.5 and 20 %, and more advantageously still between 1 and 10%.
14. Dispositif selon l'une quelconque des revendications précédentes, caracté- risé par le fait que la composition comprend, en proportion relative en poids, entre 0,1 et 30 % du polymère filmogène (B), de préférence entre 0,5 et 20 %, et plus avantageusement encore entre 1 et 10 %. 14. Device according to any one of the preceding claims, characterized in that the composition comprises, in relative proportion by weight, between 0.1 and 30% of the film-forming polymer (B), preferably between 0.5 and 20%, and more advantageously still between 1 and 10%.
15. Dispositif selon l'une quelconque des revendications précédentes, caractérisé par le fait que la composition comprend un solvant organique additionnel présent à une concentration relative en poids comprise entre 0,5 et 80 %.15. Device according to any one of the preceding claims, characterized in that the composition comprises an additional organic solvent present at a relative concentration by weight of between 0.5 and 80%.
16. Dispositif selon l'une quelconque des revendication précédentes, caractérisé par le fait que le polymère filmogène (B) est un polymère anionique choisi parmi :16. Device according to any one of the preceding claims, characterized in that the film-forming polymer (B) is an anionic polymer chosen from:
- les polymères comportant des motifs carboxyliques dérivant de monomères mono ou diacides carboxyliques insaturés de formule :- polymers comprising carboxylic units derived from mono or unsaturated dicarboxylic acid monomers of formula:
Figure imgf000036_0001
Figure imgf000036_0001
dans laquelle n est un nombre entier de 0 à 10, A désigne un groupement méthylène, éventuellement relié à l'atome de carbone du groupement insaturé ou au groupement méthylène voisin lorsque n est supérieur à 1 par l'intermédiaire d'un hétéroatome tel que oxygène ou soufre, R7 désigne un atome d'hydrogène, un groupement phényle ou benzyle, Rs désigne un atome d'hydrogène, un groupement alkyle inférieur ou carboxyle, Rg désigne un atome d'hydrogène, un groupement alkyle inférieur, un groupement -CH2-COOH, phényle ou benzyle ;in which n is an integer from 0 to 10, A denotes a methylene group, optionally linked to the carbon atom of the unsaturated group or to the neighboring methylene group when n is greater than 1 via a heteroatom such as oxygen or sulfur, R7 denotes a hydrogen atom, a phenyl or benzyl group, Rs denotes a hydrogen atom, a lower alkyl or carboxyl group, Rg denotes a hydrogen atom, a lower alkyl group, a -CH2 group -COOH, phenyl or benzyl;
- les polymères comprenant des motifs dérivant d'acide sulfonique tels que des motifs vinylsulfonique, styrènesulfonique, acrylamido alkylsulfonique.- polymers comprising units derived from sulfonic acid such as vinylsulfonic, styrenesulfonic, acrylamido alkylsulfonic units.
17. Dispositif selon la revendication précédente, caractérisé en ce que le poly- mère filmogène anionique est choisi parmi :17. Device according to the preceding claim, characterized in that the anionic film-forming polymer is chosen from:
- les copolymères d'acide acrylique tels que le terpolymère acide acryli- que/acrylate d'éthyle/N-tertiobutylacrylamide ;- acrylic acid copolymers such as the acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymer;
- les copolymères dérivés d'acide crotonique tels que les terpolymères acétate de vinyle / tertio-butyl benzoate de vinyle / acide crotonique et les terpolymères acide crotonique/acétate de vinyle/néododécanoate de vinyle ; - les polymères dérivés d'acides ou d'anhydrides maleique, fumarique, itaconique avec des esters vinyliques, des éthers vinyliques, des halogénures vinyliques, des dérivés phénylvinyliques, l'acide acrylique et ses esters tels que les copolymères méthylvinyléther/anhydride maleique mono estérifié ; - les copolymères d'acide méthacrylique et de méthacrylate de méthyle ;- copolymers derived from crotonic acid such as the vinyl acetate / vinyl tert-butyl benzoate / crotonic acid terpolymers and the crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers; - polymers derived from maleic, fumaric or itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters such as methyl vinyl ether / mono ester maleic anhydride copolymers ; - copolymers of methacrylic acid and methyl methacrylate;
- le "copolymere d'acide méthacrylique et d'acrylate d'éthyle;- the " copolymer of methacrylic acid and ethyl acrylate;
- le copolymere acétate de vinyle/acide crotonique ;- the vinyl acetate / crotonic acid copolymer;
- le terpolymère acétate de vinyle/acide crotonique/polyéthylèneglycol.- the vinyl acetate / crotonic acid / polyethylene glycol terpolymer.
18. Dispositif selon l'une quelconque des revendications 1 à 15, caractérisé en ce que le polymère filmogène (B) est un polymère amphotère choisi parmi les polymères comportant des motifs dérivant: a) d'au moins un monomère choisi parmi les acrylamides ou les méthacrylamides substitués sur l'azote par un radical alkyle, b) d'au moins un comonomère acide contenant un ou plusieurs groupements carboxyliques réactifs, et c) au moins un comonomère basique tel que des esters à substituants amine primaire, secondaire, tertiaire et quaternaire des acides acrylique et méthacrylique et le produit de quaternisation du méthacrylate de diméthyl- aminoéthyle avec le sulfate de diméthyle ou diéthyle.18. Device according to any one of claims 1 to 15, characterized in that the film-forming polymer (B) is an amphoteric polymer chosen from polymers comprising units deriving from: a) at least one monomer chosen from acrylamides or methacrylamides substituted on nitrogen by an alkyl radical, b) at least one acidic comonomer containing one or more reactive carboxylic groups, and c) at least one basic comonomer such as esters with primary, secondary, tertiary amine substituents and quaternary of acrylic and methacrylic acids and the quaternization product of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.
19. Dispositif selon l'une quelconque des revendications 1 à 15, caractérisé par le fait que le polymère filmogène (B) est un polymère non ionique choisi parmi:19. Device according to any one of claims 1 to 15, characterized in that the film-forming polymer (B) is a nonionic polymer chosen from:
- les polyalkyloxazolines; - les homopolymères d'acétate de vinyle;- polyalkyloxazolines; - vinyl acetate homopolymers;
- les copolymères d'acétate de vinyle et d'ester acrylique;- copolymers of vinyl acetate and acrylic ester;
- les copolymères d'acétate de vinyle et d'éthylène;- copolymers of vinyl acetate and ethylene;
- les copolymères d'acétate de vinyle et d'ester maléïque;- copolymers of vinyl acetate and maleic ester;
- les copolymères de polyéthylèπe et d'anhydride maléïque; - les homopolymères d'acrylates d'alkyle et les homopolymères de méthacry- lates d'alkyle; - les copolymères d'esters acryliques tels que par exemple les copolymères d'acrylates d'alkyle et de méthacrylates d'alkyle ;- the copolymers of polyethylen and maleic anhydride; - homopolymers of alkyl acrylates and homopolymers of alkyl methacrylates; - copolymers of acrylic esters such as, for example, copolymers of alkyl acrylates and alkyl methacrylates;
- les copolymères d'acrylonitrile et d'un monomère non ionique choisi par exemple parmi le butadiène et les (méth)acrylates d'alkyle; et - les copolymères d'acrylate d'alkyle et d'uréthanne.- copolymers of acrylonitrile and of a nonionic monomer chosen, for example, from butadiene and alkyl (meth) acrylates; and - copolymers of alkyl acrylate and urethane.
20. Dispositif selon l'une quelconque des revendications 1 à 15, caractérisé par le fait que le polymère filmogène (B) est un polymère cationique choisi parmi :20. Device according to any one of claims 1 to 15, characterized in that the film-forming polymer (B) is a cationic polymer chosen from:
- le copolymere d'acrylamide et de diméthylaminoéthyl méthacrylate quaternisé au sulfate de diméthyle,- the copolymer of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulphate,
- les copolymères d'acrylamide et de chlorure de méthacryloyloxyéthyltrimé- thylammonium,- copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride,
- le copolymere d'acrylamide et de méthosulfate de méthacryloyloxyéthyltrimé- thylammonium, - les copolymères vinyipyrroiidone / acrylate ou méthacrylate de dialkylami- noalkyle quaternisés ou non,- the copolymer of acrylamide and methacryloyloxyethyltrimethylammonium methosulphate, - vinyipyrroiidone / acrylate or dialkylamino-noalkyl methacrylate, quaternized or not,
- les terpolymère méthacrylate de diméthyl amino éthyle/ vinylcaprolactame/ vinyipyrroiidone,- dimethyl amino ethyl methacrylate / vinylcaprolactam / vinyipyrroiidone terpolymer,
- et le copolymere vinyipyrroiidone / methacrylamide de diméthylaminopropyle quaternisé.- And the vinyipyrroiidone / methacrylamide dimethylaminopropyl quaternized copolymer.
21. Dispositif selon l'une quelconque des revendications 1 à 15, caractérisé par le fait que le polymère filmogène (B) est un polymère silicone greffe comprenant une portion polysiloxane et une portion constituée d'une chaîne organique non siliconée.21. Device according to any one of claims 1 to 15, characterized in that the film-forming polymer (B) is a graft silicone polymer comprising a polysiloxane portion and a portion consisting of a non-silicone organic chain.
22. Dispositif selon l'une quelconque des revendications 1 à 15, caractérisé par le fait que le polymère filmogène (B) est un polyuréthanne fonctionnalisé ou non, silicone ou non différent de (A).22. Device according to any one of claims 1 to 15, characterized in that the film-forming polymer (B) is a polyurethane functionalized or not, silicone or not different from (A).
23. Dispositif selon l'une quelconque des revendications précédentes, caractérisé par le fait qu'il délivre une quantité de composition comprise entre 120 et 170 μl lorsque l'utilisateur applique 1 pression sur le bouton poussoir, et de préférence une quantité de composition comprise entre 140 et 160 μl.23. Device according to any one of the preceding claims, characterized in that it delivers an amount of composition between 120 and 170 μl when the user applies 1 press on the push button, and preferably an amount of composition between 140 and 160 μl.
24. Dispositif selon l'une quelconque des revendications précédentes, caracté- risé par le fait que la composition contient en outre des additifs cosmétiques conventionnels choisis dans le groupe comprenant les corps gras, les agents épaississants, les adoucissants, les agents anti-mousse, les agents hydratants, les agents antiperspirants, les agents alcalinisants, les colorants, les pigments, les parfums, les conservateurs, les tensioactifs, les siliconés volatiles ou non, notamment les siliconés anioniques, les polyols , les protéines et les vitamines.24. Device according to any one of the preceding claims, characterized in that the composition also contains conventional cosmetic additives chosen from the group comprising fatty substances, thickening agents, softeners, anti-foaming agents, hydrating agents, antiperspirant agents, basifying agents, dyes, pigments, perfumes, preservatives, surfactants, volatile and non-volatile silicones, in particular anionic silicones, polyols, proteins and vitamins.
25. Procédé capillaire pour la mise en forme ou le maintien de la coiffure, caractérisé par le fait qu'il comprend la mise en œuvre d'un dispositif conforme à l'une quelconque des revendications précédentes.25. Hair method for shaping or maintaining the hairstyle, characterized in that it comprises the use of a device according to any one of the preceding claims.
26. Utilisation d'un dispositif selon l'une quelconque des revendications 1 à 24 pour la fabrication d'un produit de coiffage. 26. Use of a device according to any one of claims 1 to 24 for the manufacture of a styling product.
PCT/FR1999/002585 1998-11-03 1999-10-25 Aerosol device containing a condensation polymer comprising at least a polyurethane and/or polyurea unit WO2000025736A1 (en)

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DK99950819T DK1043969T3 (en) 1998-11-03 1999-10-25 Pump bottle assembly containing a polycondensate comprising at least one polyurethane removal group
PL341481A PL198093B1 (en) 1998-11-03 1999-10-25 Aerosol device containing a polycondensate comprising at least one polyurethane and/or polyurea constituent
DE69936253T DE69936253T3 (en) 1998-11-03 1999-10-25 BOTTLE PUMP DISPENSER CONTAINS A POLYCONDENSATE WITH AT LEAST ONE POLYURETHANE GROUPING
CA002316398A CA2316398C (en) 1998-11-03 1999-10-25 Aerosol device containing a condensation polymer comprising at least a polyurethane and/or polyurea unit
AU63455/99A AU746529B2 (en) 1998-11-03 1999-10-25 Aerosol device containing a condensation polymer comprising at least a polyurethane and/or polyurea unit
EP99950819A EP1043969B2 (en) 1998-11-03 1999-10-25 Aerosol device containing a condensation polymer comprising at least a polyurethane unit
JP2000579180A JP3646149B2 (en) 1998-11-03 1999-10-25 Pump dispenser bottle apparatus comprising a polycondensate comprising at least one polyurethane and / or polyurea unit
US12/633,236 US8691200B2 (en) 1998-11-03 2009-12-08 Pump-dispenser bottle device containing a polycondensate comprising at least one polyurethane and/or polyurea unit
US12/722,656 US20100172857A1 (en) 1998-11-03 2010-03-12 Aerosol device containing a condensation polymer comprising at least a polyurethane and/or polyurea unit

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AR021227A1 (en) 2002-07-03
US20100086508A1 (en) 2010-04-08
EP1043969B1 (en) 2007-06-06
PT1043969E (en) 2007-07-26
EP1043969B2 (en) 2011-01-12
AU6345599A (en) 2000-05-22
ES2288026T5 (en) 2011-05-20
KR20010033847A (en) 2001-04-25
PL341481A1 (en) 2001-04-23
JP3646149B2 (en) 2005-05-11
CA2316398C (en) 2009-07-14
US8691200B2 (en) 2014-04-08
ATE363926T1 (en) 2007-06-15
DE69936253T2 (en) 2008-02-14
RU2203101C2 (en) 2003-04-27
EP1043969A1 (en) 2000-10-18
CN1292675A (en) 2001-04-25
CA2316398A1 (en) 2000-05-11
FR2785182B1 (en) 2002-04-12
DK1043969T3 (en) 2007-07-02
ES2288026T3 (en) 2007-12-16
CN100335029C (en) 2007-09-05
DE69936253T3 (en) 2011-09-29
JP2002528479A (en) 2002-09-03
AU746529B2 (en) 2002-05-02
PL198093B1 (en) 2008-05-30
FR2785182A1 (en) 2000-05-05
DE69936253D1 (en) 2007-07-19
US20100172857A1 (en) 2010-07-08

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